JP5643121B2 - Method for producing aryl (diolato) boranes - Google Patents

Description

  The present invention relates to a process for producing aryl (diolate) boranes.

  Aryl (diolate) boranes are important compounds as intermediates for the synthesis of biaryls, which are raw materials for medical pesticides and functional materials (for example, Non-Patent Document 1). Usually, as a method for synthesizing these boranes, a method in which metal halide or magnesium is allowed to act on an aryl halide to convert it to an aryl metal species and then reacted with an electrophilic boration reagent. However, it cannot be applied to those having a functional group sensitive to metallic lithium or magnesium.

  In recent years, as a synthesis method of 2-aryl-4,4,5,5-tetramethyl-1,3,2-dioxaborolanes, which is one of aryl (diolate) boranes, 4,4,4 ′, 4 ', 5,5,5', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (bis (pinacolato) diboron) is reacted with an aryl halide in the presence of a transition metal catalyst Methods have been disclosed (Non-Patent Documents 2 and 3). However, bis (pinacolato) diboron is limited in its use on an industrial scale because the synthetic raw material is very expensive and requires a multi-step synthesis.

  On the other hand, there has been no report on a process for producing aryl (diolate) boranes using 2,2'-bi (1,3,2-benzodioxaborol) derivatives as raw materials that are easier and cheaper to synthesize.

Chem. Rev. 1995, 95, 2457. J. et al. Organomet. Chem. 2000, 611, 392 pages. J. et al. Organomet. Chem. , 2003, 680, 3 pages.

  An object of the present invention is to provide a simple method for producing aryl (diolate) boranes.

  As a result of intensive studies to solve the above problems, the present inventors have found that a 2,2′-bi (1,3,2-benzodioxaborol) derivative and benzene in the presence of a palladium catalyst and acetate. It has been found that aryl (diolate) boranes can be produced by reacting derivatives followed by diols.

  That is, the present invention provides a compound represented by the general formula (1) in the presence of a palladium catalyst and acetate.

（式中、Ｒ^１は、水素原子または炭素数１〜４のアルキル基を示す。）で表される２，２’−ビ（１，３，２−ベンゾジオキサボロール）誘導体と一般式（２）

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) and a general formula (2)

（式中、Ｒ^２は、水素原子；フッ素原子、水酸基またはアミノ基で置換されていてもよい炭素数１〜６のアルキル基；フッ素原子で置換されていてもよい炭素数１〜４のアルコキシ基；炭素数１〜４のアルキル基で置換されていてもよいフェニルオキシ基；（炭素数１〜４のアルキル）カルボニル基；（炭素数１〜４のアルコキシ）カルボニル基；カルボキシル基；ホルミル基；水酸基；ハロゲン原子；シアノ基；炭素数１〜４のアルキル基、炭素数１〜４のアルキル基で置換されていてもよいフェニル基または（炭素数１〜４のアルキル）カルボニル基で１つないし２つ置換されていてもよいアミノ基；カルバモイル基；（フッ素原子で置換されていてもよい炭素数１〜４のアルキル）チオ基；スルファモイル基；フルオロスルホニル基；（フッ素原子で置換されていてもよいフェニル）オキシスルホニル基；またはフェニル基を示す。隣接する水酸基は、一体となって、炭素数１から３のアルキレンジオキシ基を形成してもよい。ｎは１から４を示す。Ｘは、塩素原子；臭素原子；ヨウ素原子；またはトリフルオロメチルスルホニルオキシ基を示す。）で表されるベンゼン誘導体を反応させ、次いで一般式（３）

Wherein R ² is a hydrogen atom; a C 1-6 alkyl group optionally substituted with a fluorine atom, a hydroxyl group or an amino group; a C 1-4 alkoxy optionally substituted with a fluorine atom A phenyloxy group optionally substituted by an alkyl group having 1 to 4 carbon atoms; (an alkyl having 1 to 4 carbon atoms) carbonyl group; (an alkoxy having 1 to 4 carbon atoms) carbonyl group; a carboxyl group; a formyl group A hydroxyl group, a halogen atom, a cyano group, a phenyl group optionally substituted by an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms or a (carbonyl group having 1 to 4 alkyl) carbonyl group. And an amino group that may be substituted; a carbamoyl group; (an alkyl having 1 to 4 carbon atoms that may be substituted with a fluorine atom) thio group; a sulfamoyl group; a fluorosulfonyl group; (Phenyl optionally substituted with a fluorine atom) oxysulfonyl group; or a phenyl group, adjacent hydroxyl groups may form together an alkylenedioxy group having 1 to 3 carbon atoms. Represents 1 to 4. X represents a chlorine atom, a bromine atom, an iodine atom, or a trifluoromethylsulfonyloxy group), and then reacted with a benzene derivative represented by the general formula (3)

（式中、Ｒ^３およびＲ^４は同一または異なって、水素原子またはメチル基を示す。Ａはメチレン基；ジメチルメチレン基；エチレン基；または単結合を示す。）で表されるジオール類を反応させることを特徴とする、一般式（４）

(Wherein R ³ and R ⁴ are the same or different and each represents a hydrogen atom or a methyl group. A represents a methylene group; a dimethylmethylene group; an ethylene group; or a single bond). General formula (4)

（式中、Ｒ^２、Ｒ^３、Ｒ^４、ｎおよびＡは前記と同じ内容を示す。）で表されるアリール（ジオラート）ボラン類の製造方法に関するものである。

(Wherein R ² , R ³ , R ⁴ , n, and A have the same contents as described above.) Are related to a method for producing aryl (diolate) boranes.

  The present invention is described in further detail below. First, the 2,2′-bi (1,3,2-benzodioxaborol) derivative (1), the benzene derivative (2) and the diols (3) will be described.

Examples of the 2,2′-bi (1,3,2-benzodioxaborol) derivative (1) that can be used in this reaction include commercially available products and compounds that can be produced by known methods. be able to. Specifically, as the linear or branched alkyl group having 1 to 4 carbon atoms represented by R ¹ of the 2,2′-bi (1,3,2-benzodioxaborole) derivative (1), , Methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group and the like. R ¹ may be any of the above alkyl groups or hydrogen atoms, but is preferably a hydrogen atom or a tert-butyl group, more preferably a hydrogen atom in terms of easy availability of raw materials and a good yield.

Examples of the benzene derivative (2) of the present invention include commercially available products and compounds that can be produced by known methods. Specifically, the alkyl group having 1 to 6 carbon atoms in R ² of the benzene derivative (2) may be linear or branched, and may be a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group. , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, neopentyl group and the like. These alkyl groups may be substituted with a fluorine atom, an amino group or a hydroxyl group, specifically, a trifluoromethyl group, a difluoromethyl group, a fluoromethyl group, a 2,2,2-trifluoroethyl group, 1,1,1,3,3,3-hexafluoroisopropyl group, 2-aminoethyl group, 3-aminopropyl group, 4-aminobutyl group, 5-aminopentyl group, 6-aminohexyl group, 2-hydroxy Examples thereof include an ethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a 5-hydroxypentyl group, and a 6-hydroxyhexyl group.

The alkoxy group having 1 to 4 carbon atoms in R ² may be linear or branched, and is a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butyloxy group, tert-butyloxy group. Can be illustrated. These alkoxy groups may be substituted with a fluorine atom, such as a trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 1,1,1,3,3,3-hexafluoroisopropoxy group, etc. Can be illustrated.

Examples of the phenyloxy group which may be substituted with an alkyl group having 1 to 4 carbon atoms represented by R ² include a phenyloxy group, an o-tolyloxy group, an m-tolyloxy group, a p-tolyloxy group, and 4-ethylphenyl. Examples thereof include an oxy group, a 4-propylphenyloxy group, and a 4-butylphenyloxy group.

The (alkyl group having 1 to 4 carbon atoms) carbonyl group represented by R ² may be linear or branched, and may be an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, sec- Examples thereof include a butylcarbonyl group and a pivaloyl group.

The (carbonyl group having 1 to 4 carbon atoms) carbonyl group represented by R ² may be linear or branched, and is a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group. , Isobutoxycarbonyl group, sec-butoxycarbonyl group, and tert-butoxycarbonyl group.

Examples of the halogen atom represented by R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

1 to ² of an alkyl group having 1 to 4 carbon atoms, a phenyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or a (alkyl having 1 to 4 carbon atoms) carbonyl group represented by R 2 The alkyl group of the amino group which may be substituted may be either linear or branched. 1 to 2 carbon atoms may be substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group that may be substituted with an alkyl group with 1 to 4 carbon atoms, or a (alkyl having 1 to 4 carbon atoms) carbonyl group. Specifically, the amino group is an amino group, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, a sec-butylamino group, a tert-butylamino group, a dimethylamino group, or a diethylamino group. , Dipropylamino group, dibutylamino group, ethylmethylamino group, methylpropylamino group, butylmethylamino group, phenylamino group, diphenylamino group, bis (p-tolyl) amino group, bis (m-tolyl) amino group Bis (o-tolyl) amino group, dinaphthylamino group, naphthylphenylamino group, methylphenylamino group Acetylamino group, propionylamino group, butyrylamino group, isobutyrylamino group, valerylamino group, isovalerylamino rear Minoru group, sec- butyl carbonylamino group, pivaloylamino group and the like.

The alkyl group of the thio group (alkyl having 1 to 4 carbon atoms which may be substituted with a fluorine atom) represented by R ² may be either linear or branched. (C1-C4 alkyl optionally substituted with a fluorine atom) The thio group is specifically a methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, sec-butylthio group, tert- Examples include butylthio group, trifluoromethylthio group, 2,2,2-trifluoroethylthio group, 1,1,3,3,3-hexafluoroisopropylthio group.

Specific examples of the oxysulfonyl group represented by R ² (phenyl optionally substituted with a fluorine atom) include a phenyloxysulfonyl group, a 4-fluorophenyloxysulfonyl group, a 3-fluorophenyloxysulfonyl group, 2-fluorophenyloxysulfonyl group, 3,5-difluorophenyloxysulfonyl group, 3,4-difluorophenyloxysulfonyl group, 2,4,6-trifluorophenyloxysulfonyl group, 2,3,4,5,6 -A pentafluorophenyloxysulfonyl group etc. can be illustrated.

When R ² is an adjacent hydroxyl group, these may be combined to form an alkylenedioxy group having 1 to 3 carbon atoms. Specifically, a methylenedioxy group, an ethylenedioxy group, A propylene dioxy group etc. can be illustrated.

  X of the benzene derivative (2) is preferably a bromine atom in terms of good yield.

Examples of the diols (3) represented by the combination of R ³ , R ⁴ and A include 1,2-ethanediol, 1,3-propanediol, 2,3-butanediol, 2,3-dimethyl-2, 3-butanediol, catechol, 2,2-dimethyl-1,3-propanediol, 2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-hexanediol, 2,5 -Dimethyl-2,5-hexanediol etc. can be illustrated.

  Next, the manufacturing method of this invention is demonstrated. The production method of the present invention comprises a step 1 of reacting a 2,2′-bi (1,3,2-benzodioxaborol) derivative (1) and a benzene derivative (2) in the presence of a palladium catalyst and an acetate. Then, the step 2 comprises reacting the diols (3).

  The reaction of step 1 can be carried out in a solvent. Solvents that can be used include ether solvents such as tetrahydrofuran, diethyl ether, cyclopentyl methyl ether, methyl-tert-butyl ether, 1,2-dimethoxyethane, N, N-dimethylformamide, N-methylformamide, N-methyl. Amido solvents such as pyrrolidone, 1,3-dimethyl-2-imidazolidone, sulfoxide solvents such as dimethyl sulfoxide, diethyl sulfoxide, methanol, ethanol, propanol, 2-propanol, ethylene glycol, isopropyl alcohol, butanol, sec-butyl alcohol , Alcohol solvents such as tert-butyl alcohol, cyclohexanol, hexanol and trifluoroethanol, and nitrile solvents such as acetonitrile and propionitrile. And organic solvents like, can be exemplified water. Furthermore, these mixed solvents can be illustrated. More specifically, dimethyl sulfoxide, N, N-dimethylformamide, 1,2-dimethoxyethane, ethanol, tert-butyl alcohol, a mixed solvent of ethanol and dimethyl sulfoxide, a mixed solvent of tert-butyl alcohol and dimethyl sulfoxide, ethanol A mixed solvent of water and water is preferred. There is no restriction | limiting in particular in the usage-amount of a solvent.

  It is essential to perform the reaction of Step 1 in the presence of a palladium catalyst. Palladium compounds that can be used include dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, bis (diphenylphosphinomethane) palladium. Bis (diphenylphosphinoethane) palladium, bis (diphenylphosphinobutane) palladium, bis (diphenylphosphinopropane) palladium, bis (diphenylphosphinoferrocene) palladium, tris [tri (tert-butyl) phosphine] palladium, dichlorobis Phosphine coordinated palladium complexes such as [tri (tert-butyl) phosphine)] palladium, dibromobis [tri (tert-butyl) phosphine)] palladium It can be shown.

  These phosphine coordinated palladium complexes, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium, palladium chloride, dichloro (1,5-cyclooctadiene) palladium, palladium acetate, (π-allyl) chloropalladium, Palladium compounds such as bis (acetylacetonato) palladium and palladium bromide, triphenylphosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, tri-tert-butylphosphine, tri Cyclohexylphosphine, 1,2-bis (2,5-diethylphosphorano) ethane, cyclohexyldiphenylphosphine, methyldiphenylphosphine Ethyldiphenylphosphine, propyldiphenylphosphine, isopropyldiphenylphosphine, butyldiphenylphosphine, isobutyldiphenylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) ) -2 ′-(N, N-dimethylamino) biphenyl, 1,2-bis (2,5-dimethylphosphorano) benzene, 1,1′-bis (diisopropylphosphino) ferrocene, 1,2-bis ( 2,5-diisopropylphosphorano) benzene, 1,2-bis (2,5-diisopropylphosphorano) benzene, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2- (Dicyclohex Silphosphino) -2′-methylbiphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) ) Butane, 1,4-bis (diphenylphosphino) pentane, 1,1′-bis (diphenylphosphino) ferrocene, cis-1,2-bis (diphenylphosphino) ethylene, bis (2-diphenylphosphinoethyl) ) Phenylphosphine, 1,2-bis (diphenylphosphino) propane, tris (3,5-dimethylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,4,6-trimethoxyphenyl) phosphine, Tri (m-tolyl) phosphine, tri (o-tolyl) phosphine Tri (p-tolyl) phosphine, 1,2-bis (diphenylphosphino) benzene, 2,2′-bis (diphenylphosphino) -1,1′-biphenyl, bis (2-methoxyphenyl) phenylphosphine, 1 , 2-bis (diphenylphosphino) benzene, 1- [2- (diphenylphosphino) ferrocenyl] ethyldi-tert-butylphosphine, 2-dicyclohexylphosphino-2 ′-(N, N-dimethylamino) biphenyl, tris (Trimethylsilyl) phosphine, 2-di-tert-butylphosphino-2 ′-(N, N-dimethylamino) biphenyl, 2-di-tert-butylphosphino-2′-methylbiphenyl, 2- (dicyclohexylphosphino ) Biphenyl and 2- (dicyclohexylphosphino) -2 ', ', It can be used a palladium catalyst which is a combination of a tertiary phosphine such as 6'-triisopropyl-1,1'-biphenyl. When using a palladium catalyst in which a phosphine coordination palladium complex or a palladium compound and a tertiary phosphine are combined, the molar ratio of palladium and tertiary phosphine is not particularly limited, but is preferably 0.1 to 100 in terms of good yield. 0.5 to 5 is more preferable.

  As a palladium catalyst, dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, Palladium catalyst combining dichlorobis (acetonitrile) palladium, palladium chloride or palladium acetate and triphenylphosphine is preferred.

  There is no restriction | limiting in particular in the usage-amount of a palladium catalyst, even if it is what is called a catalyst amount, reaction will fully advance and the target object can be obtained with a sufficient yield.

  It is essential to carry out the reaction of step 1 in the presence of acetate. Examples of acetates that can be used include alkali metal acetates such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate, alkaline earth metal acetates such as magnesium acetate and calcium acetate, copper acetate, and silver acetate. Examples include 1B group metal acetates, and mixtures thereof may be used. In terms of good yield, alkali metal salts are preferred, and sodium acetate, potassium acetate and mixtures thereof are more preferred.

  Although there is no restriction | limiting in particular in the usage-amount of acetate, It is preferable to use 1 equivalent or more with respect to a benzene derivative (2) at a point with a sufficient yield.

  Although there is no restriction | limiting in particular in the reaction temperature of reaction of the process 1, Reaction can be implemented at the temperature chosen suitably from the temperature of -100-200 degreeC, and it is carried out at 80-140 degreeC at a point with a sufficient yield. desirable. There is no particular limitation on the reaction time.

  There is no restriction | limiting in particular in the usage-amount of a 2,2'-bi (1,3,2- benzodioxaborole) derivative (1), A yield is good by using 1 equivalent or more with respect to a benzene derivative (2). The reaction proceeds.

  The reaction of step 2 can be carried out in a solvent. Solvents that can be used include ether solvents such as tetrahydrofuran, diethyl ether, cyclopentyl methyl ether, methyl-tert-butyl ether, 1,2-dimethoxyethane, N, N-dimethylformamide, N-methylformamide, N-methyl. Amido solvents such as pyrrolidone, 1,3-dimethyl-2-imidazolidone, sulfoxide solvents such as dimethyl sulfoxide, diethyl sulfoxide, methanol, ethanol, propanol, 2-propanol, ethylene glycol, isopropyl alcohol, butanol, sec-butyl alcohol , Alcohol solvents such as tert-butyl alcohol, cyclohexanol, hexanol and trifluoroethanol, and nitrile solvents such as acetonitrile and propionitrile. And organic solvents like, can be exemplified water. Furthermore, these mixed solvents can be illustrated. More specifically, dimethyl sulfoxide, N, N-dimethylformamide, 1,2-dimethoxyethane, ethanol, tert-butyl alcohol, a mixed solvent of ethanol and dimethyl sulfoxide, a mixed solvent of tert-butyl alcohol and dimethyl sulfoxide, ethanol A mixed solvent of water and water is preferred.

  From the viewpoint of convenience, it is preferable to carry out the reaction of Step 2 using the solvent of Step 1 as it is. There is no restriction | limiting in particular in the usage-amount of a solvent.

  There is no restriction | limiting in particular in the usage-amount of diol (3), Reaction progresses with sufficient yield by using 1 equivalent or more with respect to a benzene derivative (2).

  Although there is no restriction | limiting in particular in the reaction temperature of reaction of the process 2, Reaction can be implemented at the temperature selected suitably from the temperature of -100-100 degreeC, and it can carry out at 0-50 degreeC at a point with a sufficient yield. desirable. There is no particular limitation on the reaction time.

  There is no particular limitation on the method for isolating aryl (diolate) boranes (4), and general-purpose methods such as solvent extraction, column chromatography, preparative thin layer chromatography, preparative liquid chromatography, recrystallization, distillation or sublimation The object can be obtained by the method.

  INDUSTRIAL APPLICABILITY According to the present invention, aryl (diolate) boranes useful for the synthesis of medical pesticides and electronic materials can be obtained by a simple production method.

  EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited to these.

  Example-1

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ安息香酸メチル（１．００ｍｍｏｌ，２１５ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮した。得られた残渣を蒸留することにより、白色固体の４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルを得た（２５２ｍｇ，収率９６％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３６（１２Ｈ，ｓ），３．９２（３Ｈ，ｓ），７．８７（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ），８．０２（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ）．
ＭＳ（ｍ／ｚ）：２６２［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, methyl 4-bromobenzoate (1.00 mmol, 215 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, water was added to the reaction mixture and extracted with hexane. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated. The obtained residue was distilled to obtain methyl 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate (252 mg, yield). 96%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.36 (12H, s), 3.92 (3H, s), 7.87 (2H, d, J = 8.4 Hz), 8.02 (2H, d, J = 8.4 Hz).
MS (m / z): 262 [M] ^<+> .

Example-2
The same operation was performed except that dimethyl sulfoxide (6.0 mL) was used instead of ethanol (6.0 mL) in Example 1, and 4- (4,4,5,5-tetramethyl-1, The formation of methyl 3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 56%).

Example-3
The same operation was performed except that ethanol (3.0 mL) and dimethyl sulfoxide (3.0 mL) were used instead of ethanol (6.0 mL) in Example 1, and 4- (4, 4, 5 , 5-Tetramethyl-1,3,2-dioxaborolan-2-yl) methyl benzoate was confirmed by ¹ H NMR (NMR yield 82%).
Example-4
The same operation was performed except that tert-butyl alcohol (3.0 mL) and dimethyl sulfoxide (3.0 mL) were used instead of ethanol (6.0 mL) in Example 1, and 4- (4, The formation of methyl 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 46%).

Example-5
All the same operations were carried out except that potassium acetate of Example-1 was changed to 1.0 mmol (98 mg), and 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl was used. ) Production of methyl benzoate was confirmed by ¹ H NMR (NMR yield 53%).

Example-6
All the same operations were carried out except that potassium acetate of Example-1 was changed to 2.00 mmol (196 mg), and 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl was used. ) Production of methyl benzoate was confirmed by ¹ H NMR (NMR yield 91%).

Example-7
All the same operations were performed except that potassium acetate of Example-1 was changed to 2.50 mmol (245 mg), and 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl was used. ) Production of methyl benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example-8
The same operation was performed except that potassium acetate (1.50 mmol, 147 mg) and sodium acetate (1.50 mmol, 123 mg) were used in place of the potassium acetate of Example-1, and 4- (4, 4, 5 , 5-Tetramethyl-1,3,2-dioxaborolan-2-yl) methyl benzoate was confirmed by ¹ H NMR (NMR yield 97%).

Example-9
The same operation was carried out except that potassium acetate (0.40 mmol, 39 mg) and sodium acetate (2.60 mmol, 213 mg) were used in place of the potassium acetate of Example-1, and 4- (4, 4, 5 , 5-Tetramethyl-1,3,2-dioxaborolan-2-yl) methyl benzoate was confirmed by ¹ H NMR (NMR yield 97%).

Example-10
The same operation was performed except that sodium acetate (3.00 mmol, 246 mg) was used in place of the potassium acetate of Example-1, and 4- (4,4,5,5-tetramethyl-1,3,3) was used. The formation of methyl 2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 98%).

Example-11
Instead of dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium in Example-1, dichlorobis (acetonitrile) palladium (0.03 mmol, 8 mg) and triphenylphosphine (0.03 mmol, 8 mg) were used. Except for the above, the same operation was carried out, and the formation of methyl 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR Yield 83%).

Example-12
Except for using dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium in Example-1 and using palladium acetate (0.03 mmol, 7 mg) and triphenylphosphine (0.03 mmol, 8 mg). All the same operations were performed, and the formation of methyl 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 71). %).

Example-13
In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. To this reaction solution, methyl 4-bromobenzoate (1.00 mmol, 215 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, water was added to the reaction mixture and extracted with hexane. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated. The obtained residue was distilled to obtain methyl 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate (252 mg, yield). 96%).

Example-14
The same operation was performed except that dichlorobis (triphenylphosphine) palladium (0.030 mmol, 21 mg) was used instead of dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium in Example-13. , Methyl 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example-15
The same operation was carried out except that tetrakis (triphenylphosphine) palladium (0.030 mmol, 35 mg) was used instead of dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium in Example-13. , 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 97%).

Example-16
Except for using dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium in Example-13, palladium chloride (0.03 mmol, 5 mg) and triphenylphosphine (0.060 mmol, 16 mg) were used. All the same operations were performed, and the formation of methyl 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99). %).

Example-17
Instead of dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium in Example-13, dichlorobis (acetonitrile) palladium (0.03 mmol, 5 mg) and triphenylphosphine (0.060 mmol, 16 mg) were used. Except for the above, the same operation was carried out, and the formation of methyl 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR Yield 96%).

Example-18
The same procedure was repeated except that ethanol (6.0 mL) was used instead of dimethyl sulfoxide in Example-13, and 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used. The formation of methyl-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example-19
The same operation was performed except that tert-butyl alcohol (6.0 mL) was used instead of dimethyl sulfoxide in Example-13, and 4- (4,4,5,5-tetramethyl-1,3,3) was used. The formation of methyl 2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 64%).

Example-20
The same operation was carried out except that ethanol (3.0 mL) and dimethyl sulfoxide (3.0 mL) were used instead of dimethyl sulfoxide in Example-13, and 4- (4,4,5,5-tetramethyl was used. The formation of methyl -1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example-21
The same operation was performed except that ethanol (3.0 mL) and water (3.0 mL) were used instead of dimethyl sulfoxide in Example-13, and 4- (4,4,5,5-tetramethyl- The formation of methyl 1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 69%).

Example-22
The same operation was performed except that tert-butyl alcohol (3.0 mL) and dimethyl sulfoxide (3.0 mL) were used instead of dimethyl sulfoxide in Example-13, and 4- (4, 4, 5, 5 -The formation of methyl tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 94%).

Example-23
The same operation was performed except that sodium acetate (7.2 mmol, 591 mg) was used instead of potassium acetate in Example-13, and 4- (4,4,5,5-tetramethyl-1,3,3) was used. The formation of methyl 2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 52%).

Example-24
The same operation was performed except that potassium acetate (3.6 mmol, 353 mg) and sodium acetate (3.6 mmol, 295 mg) were used instead of potassium acetate in Example-13, and 4- (4, 4, 5 , 5-Tetramethyl-1,3,2-dioxaborolan-2-yl) methyl benzoate was confirmed by ¹ H NMR (NMR yield 99%).

  Example-25

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモアセトフェノン（１．０ｍｍｏｌ，１９９ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮した。得られた残渣を蒸留することにより、白色固体の１−［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］エタノンを得た（１８９ｍｇ，収率７７％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３６（１２Ｈ，ｓ），２．６２（３Ｈ，ｓ），７．８９（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ），７．９３（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ）．
ＭＳ（ｍ／ｚ）：２４６［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 4-Bromoacetophenone (1.0 mmol, 199 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, water was added to the reaction mixture and extracted with hexane. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated. The obtained residue was distilled to obtain 1- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] ethanone as a white solid (189 mg). Yield 77%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.36 (12H, s), 2.62 (3H, s), 7.89 (2H, d, J = 8.4 Hz), 7.93 (2H, d, J = 8.4 Hz).
MS (m / z): 246 [M] ^<+> .

Example-26
The same operation was performed except that the potassium acetate of Example-25 was 7.2 mmol (706 mg) and dimethyl sulfoxide (6.0 mL) was used instead of ethanol, and 1- [4- (4,4,5 , 5-Tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] ethanone was confirmed by ¹ H NMR (NMR yield 91%).

  Example-27

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に１−ブロモ−４−クロロベンゼン（１．００ｍｍｏｌ，１９１ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮した。得られた残渣を蒸留することにより、白色固体の２−（４−クロロフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランを得た（１９６ｍｇ，収率８２％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３４（１２Ｈ，ｓ），７．３４（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ），７．７３（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ）．
ＭＳ（ｍ／ｚ）：２３９［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 1-Bromo-4-chlorobenzene (1.00 mmol, 191 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, water was added to the reaction mixture and extracted with hexane. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated. The obtained residue was distilled to obtain 2- (4-chlorophenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (196 mg, yield 82%) as a white solid. .
¹ H-NMR (deuterated chloroform, ppm): δ 1.34 (12H, s), 7.34 (2H, d, J = 8.4 Hz), 7.73 (2H, d, J = 8.4 Hz).
MS (m / z): 239 [M] ^<+> .

Example-28
The same procedure was followed except that the potassium acetate of Example-27 was 7.20 mmol (706 mg) and dimethyl sulfoxide (6.0 mL) was used instead of ethanol, and 2- (4-chlorophenyl) -4,4 , 5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 99%).

Example-29
The same procedure as in Example 27 was carried out except that the potassium acetate in Example 27 was 7.20 mmol (706 mg) and N, N-dimethylformamide (6.0 mL) was used instead of ethanol. 2- (4-Chlorophenyl) Formation of -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 94%).

Example-30
The same procedure was performed except that the potassium acetate of Example-27 was 7.20 mmol (706 mg) and 1,2-dimethoxyethane (6.0 mL) was used instead of ethanol, and 2- (4-chlorophenyl) Formation of -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 37%).

  Example-31

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモベンゾニトリル（１．００ｍｍｏｌ，１８２ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮した。得られた残渣を蒸留することにより、白色固体の４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゾニトリルを得た（１９２ｍｇ，収率８４％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３５（１２Ｈ，ｓ），７．６４（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ），７．８８（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ）．
ＭＳ（ｍ／ｚ）：２２９［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 4-Bromobenzonitrile (1.00 mmol, 182 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, water was added to the reaction mixture and extracted with hexane. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated. The obtained residue was distilled to obtain 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzonitrile as a white solid (192 mg, yield 84). %).
¹ H-NMR (deuterated chloroform, ppm): δ 1.35 (12H, s), 7.64 (2H, d, J = 8.4 Hz), 7.88 (2H, d, J = 8.4 Hz).
MS (m / z): 229 [M] ^<+> .

Example-32
The same procedure as in Example 31 was performed except that 7.2 mmol (706 mg) of potassium acetate was used and dimethyl sulfoxide (6.0 mL) was used instead of ethanol. 4- (4, 4, 5, 5- The formation of tetramethyl-1,3,2-dioxaborolan-2-yl) benzonitrile was confirmed by ¹ H NMR (NMR yield 99%).

  Example-33

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモフェノール（１．００ｍｍｏｌ，１７３ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮した。得られた残渣を蒸留することにより、白色固体の４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェノールを得た（９７ｍｇ，収率４４％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３３（１２Ｈ，ｓ），４．７９（１Ｈ，ｓ），６．８２（２Ｈ，ｄ，Ｊ＝８．６Ｈｚ），７．７１（２Ｈ，ｄ，Ｊ＝８．６Ｈｚ）．
ＭＳ（ｍ／ｚ）：２２０［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 4-Bromophenol (1.00 mmol, 173 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, water was added to the reaction mixture and extracted with hexane. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated. The obtained residue was distilled to obtain 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenol as a white solid (97 mg, yield 44%). ).
¹ H-NMR (deuterated chloroform, ppm): δ1.33 (12H, s), 4.79 (1H, s), 6.82 (2H, d, J = 8.6 Hz), 7.71 (2H, d, J = 8.6 Hz).
MS (m / z): 220 [M] ^&lt; ^{+ &gt};.

Example-34
The same procedure as in Example 33 was performed except that 7.2 mmol (706 mg) of potassium acetate was used and dimethyl sulfoxide (6.0 mL) was used instead of ethanol. 4- (4, 4, 5, 5- The formation of tetramethyl-1,3,2-dioxaborolan-2-yl) phenol was confirmed by ¹ H NMR (NMR yield 52%).

  Example-35

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモアニソール（１．００ｍｍｏｌ，１８７ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮した。得られた残渣を蒸留することにより、無色液体の２−（４−メトキシフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランを得た（２２２ｍｇ，収率９５％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３３（１２Ｈ，ｓ），３．８３（３Ｈ，ｓ），６．８９（２Ｈ，ｄ，Ｊ＝８．７Ｈｚ），７．７５（２Ｈ，ｄ，Ｊ＝８．７Ｈｚ）．
ＭＳ（ｍ／ｚ）：２３４［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 4-Bromoanisole (1.00 mmol, 187 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, water was added to the reaction mixture and extracted with hexane. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated. The resulting residue was distilled to obtain colorless liquid 2- (4-methoxyphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (222 mg, 95% yield). ).
¹ H-NMR (deuterated chloroform, ppm): δ1.33 (12H, s), 3.83 (3H, s), 6.89 (2H, d, J = 8.7 Hz), 7.75 (2H, d, J = 8.7 Hz).
MS (m / z): 234 [M] ^<+> .

Example-36
The same procedure as in Example 35 was performed except that potassium acetate in Example 35 was 7.20 mmol (706 mg) and dimethyl sulfoxide (6.0 mL) was used instead of ethanol, and 2- (4-methoxyphenyl) -4, Formation of 4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 98%).

  Example-37

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に（４−ブロモフェニル）ジフェニルアミン（１．００ｍｍｏｌ，３２４ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮した。得られた残渣を蒸留することにより、白色固体のジフェニル［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］アミンを得た（２７５ｍｇ，収率７４％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３３（１２Ｈ，ｓ），７．０２（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ），７．０４（３Ｈ，ｔ，Ｊ＝７．５Ｈｚ），７．１０（４Ｈ，ｄ，Ｊ＝７．８Ｈｚ），７．２７−７．２３（３Ｈ，ｍ），７．６６（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ）．
ＭＳ（ｍ／ｚ）：３７１［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. (4-Bromophenyl) diphenylamine (1.00 mmol, 324 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, water was added to the reaction mixture and extracted with hexane. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated. The obtained residue was distilled to obtain white solid diphenyl [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] amine (275 mg, Yield 74%).
¹ H-NMR (deuterated chloroform, ppm): δ1.33 (12H, s), 7.02 (2H, d, J = 8.5 Hz), 7.04 (3H, t, J = 7.5 Hz), 7.10 (4H, d, J = 7.8 Hz), 7.27-7.23 (3H, m), 7.66 (2H, d, J = 8.5 Hz).
MS (m / z): 371 [M] ^<+> .

Example-38
The same operation was carried out except that the potassium acetate of Example-37 was adjusted to 3.00 mmol (294 mg) and ethanol (6.0 mL) was used instead of dimethyl sulfoxide, and diphenyl [4- (4, 4, 5, The formation of 5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] amine was confirmed by ¹ H NMR (NMR yield 85%).

  Example-39

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に（４−ブロモフェニル）フェニル エーテル（１．００ｍｍｏｌ，２４９ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮した。得られた残渣を蒸留することにより、無色液体のフェニル［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）］フェニル エーテルを得た（１４５ｍｇ，収率４９％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）： δ１．３４（１２Ｈ，ｓ），６．９８（２Ｈ，ｄ，Ｊ＝８．６Ｈｚ），７．０１−７．０３（２Ｈ，ｍ），７．１３（１Ｈ，ｔｔ，Ｊ＝１．０，７．４Ｈｚ），７．３２−７．３７（２Ｈ，ｍ），７．７８（２Ｈ，ｄ，Ｊ＝８．６Ｈｚ）．
ＭＳ（ｍ／ｚ）：２９６［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. (4-Bromophenyl) phenyl ether (1.00 mmol, 249 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, water was added to the reaction mixture and extracted with hexane. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated. The resulting residue was distilled to obtain colorless liquid phenyl [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)] phenyl ether (145 mg, Yield 49%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.34 (12H, s), 6.98 (2H, d, J = 8.6 Hz), 7.01-7.03 (2H, m), 7. 13 (1H, tt, J = 1.0, 7.4 Hz), 7.32-7.37 (2H, m), 7.78 (2H, d, J = 8.6 Hz).
MS (m / z): 296 [M] ^<+> .

Example-40
The same operation was carried out except that the potassium acetate of Example-39 was adjusted to 3.00 mmol (294 mg) and ethanol (6.0 mL) was used instead of dimethyl sulfoxide, and phenyl [4- (4, 4, 5, The formation of 5-tetramethyl-1,3,2-dioxaborolan-2-yl)] phenyl ether was confirmed by ¹ H NMR (NMR yield 65%).

  Example-41

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に１−ブロモ−３，５−ジメチルベンゼン（１．００ｍｍｏｌ，１８５ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮した。得られた残渣を蒸留することにより、白色固体の２−（３，５−ジメチルフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランを得た（１６７ｍｇ，収率７２％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３４（１２Ｈ，ｓ），２．３２（６Ｈ，ｓ），７．１０（１Ｈ，ｓ），７．４４（２Ｈ，ｓ）．
ＭＳ（ｍ／ｚ）：２３２［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 1-Bromo-3,5-dimethylbenzene (1.00 mmol, 185 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, water was added to the reaction mixture and extracted with hexane. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated. The obtained residue was distilled to obtain 2- (3,5-dimethylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (167 mg, yield) as a white solid. 72%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.34 (12H, s), 2.32 (6H, s), 7.10 (1H, s), 7.44 (2H, s).
MS (m / z): 232 [M] ^<+> .

Example-42
The same procedure was performed except that ethanol potassium (6.0 mL) was used instead of dimethyl sulfoxide in an amount of 3.00 mmol (294 mg) of potassium acetate in Example-41, and 2- (3,5-dimethylphenyl)- Formation of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 99%).

  Example-43

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ−Ｎ，Ｎ−ジメチルアニリン（１．００ｍｍｏｌ，２００ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲによりＮ，Ｎ−ジメチル−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）アニリンの生成を確認した（ＮＭＲ収率：４４％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３２（１２Ｈ，ｓ），２．９８（６Ｈ，ｓ），６．６８（２Ｈ，ｄ，Ｊ＝８．８Ｈｚ），７．６７（２Ｈ，ｄ，Ｊ＝８．８Ｈｚ）．
ＭＳ（ｍ／ｚ）：２４７［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 4-Bromo-N, N-dimethylaniline (1.00 mmol, 200 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. ¹ H NMR confirmed the formation of N, N-dimethyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline (NMR yield: 44%). .
¹ H-NMR (deuterated chloroform, ppm): δ 1.32 (12H, s), 2.98 (6H, s), 6.68 (2H, d, J = 8.8 Hz), 7.67 (2H, d, J = 8.8 Hz).
MS (m / z): 247 [M] ^<+> .

  Example-44

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ安息香酸メチル（１．００ｍｍｏｌ，２１５ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、１，２−エタンジオール（２．２０ｍｍｏｌ，１３７ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより４−（１，３，２−ジオキサボロラン−２−イル）安息香酸メチルの生成を確認した（ＮＭＲ収率：９９％）。反応混合物にジエチルエーテルを加えろ過し、ろ液を濃縮した。ヘキサンで抽出し、ろ液を濃縮し、無色液体の４−（１，３，２−ジオキサボロラン−２−イル）安息香酸メチルを得た（１８３ｍｇ，収率８９％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ３．９３（３Ｈ，ｓ），４．４１（４Ｈ，ｓ），７．８８（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ），８．０４（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ）．
ＭＳ（ｍ／ｚ）：２０６［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, methyl 4-bromobenzoate (1.00 mmol, 215 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 1,2-ethanediol (2.20 mmol, 137 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. Formation of methyl 4- (1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield: 99%). Diethyl ether was added to the reaction mixture and filtered, and the filtrate was concentrated. Extraction with hexane was performed, and the filtrate was concentrated to obtain methyl 4- (1,3,2-dioxaborolan-2-yl) benzoate as a colorless liquid (183 mg, yield 89%).
¹ H-NMR (deuterated chloroform, ppm): δ 3.93 (3H, s), 4.41 (4H, s), 7.88 (2H, d, J = 8.4 Hz), 8.04 (2H, d, J = 8.4 Hz).
MS (m / z): 206 [M] ^&lt; ^{+ &gt};.

Example-45
The same procedure as in Example 44 was conducted except that 7.2 mmol (706 mg) of potassium acetate was used and dimethyl sulfoxide (6.0 mL) was used instead of ethanol. 4- (1,3,2-dioxaborolane- The formation of 2-yl) methyl benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example-46
In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichlorobis (triphenylphosphine) palladium (0.030 mmol, 21 mg), potassium acetate (7 20 mmol, 706 mg) was added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. To this reaction solution, methyl 4-bromobenzoate (1.00 mmol, 215 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 1,2-ethanediol (2.20 mmol, 137 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. Formation of methyl 4- (1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

  Example-47

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ安息香酸メチル（１．００ｍｍｏｌ，２１５ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、１，３−プロパンジオール（２．２０ｍｍｏｌ，１６３ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより４−（１，３，２−ジオキサボリナン−２−イル）安息香酸メチルの生成を確認した（ＮＭＲ収率：９９％）。反応混合物にジエチルエーテルを加えろ過し、ろ液を濃縮した。ヘキサンで抽出し、ろ液を濃縮し、無色液体の４−（１，３，２−ジオキサボリナン−２−イル）安息香酸メチルを得た（１８９ｍｇ，収率８６％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ２．０８（２Ｈ，ｑｕｉｎｔ，Ｊ＝５．５Ｈｚ），３．９２（３Ｈ，ｓ），４．１８（４Ｈ，ｔ，Ｊ＝５．５Ｈｚ），７．８３（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ），８．００（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ）．
ＭＳ（ｍ／ｚ）：２２０［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, methyl 4-bromobenzoate (1.00 mmol, 215 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 1,3-propanediol (2.20 mmol, 163 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. The production of methyl 4- (1,3,2-dioxaborinan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield: 99%). Diethyl ether was added to the reaction mixture and filtered, and the filtrate was concentrated. Extraction with hexane was performed, and the filtrate was concentrated to obtain methyl 4- (1,3,2-dioxaborin-2-yl) benzoate (189 mg, yield 86%) as a colorless liquid.
¹ H-NMR (deuterated chloroform, ppm): δ 2.08 (2H, quint, J = 5.5 Hz), 3.92 (3H, s), 4.18 (4H, t, J = 5.5 Hz), 7.83 (2H, d, J = 8.4 Hz), 8.00 (2H, d, J = 8.4 Hz).
MS (m / z): 220 [M] ^&lt; ^{+ &gt};.

Example-48
The same operation was carried out except that dichlorobis (triphenylphosphine) palladium (0.030 mmol, 21 mg) was used instead of dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium in Example-47, Formation of methyl 4- (1,3,2-dioxaborinan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example-49
The same procedure was followed except that the potassium acetate of Example-47 was 7.20 mmol (706 mg) and dimethyl sulfoxide (6.0 mL) was used instead of ethanol, and 4- (1,3,2-dioxaborinane- The formation of 2-yl) methyl benzoate was confirmed by ¹ H NMR (NMR yield 99%).

  Example-50

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ安息香酸メチル（１．００ｍｍｏｌ，２１５ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，２−ジメチル−１，３−プロパンジオール（２．２０ｍｍｏｌ，２２９ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより４−（５，５−ジメチル−１，３，２−ジオキサボリナン−２−イル）安息香酸メチルの生成を確認した（ＮＭＲ収率９９％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．０３（６Ｈ，ｓ），３．７９（４Ｈ，ｓ），３．９２（３Ｈ，ｓ），７．８６（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），８．００（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）．
ＭＳ（ｍ／ｚ）：２４８［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, methyl 4-bromobenzoate (1.00 mmol, 215 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,2-dimethyl-1,3-propanediol (2.20 mmol, 229 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. ¹ H NMR confirmed the formation of methyl 4- (5,5-dimethyl-1,3,2-dioxaborin-2-yl) benzoate (NMR yield 99%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.03 (6H, s), 3.79 (4H, s), 3.92 (3H, s), 7.86 (2H, d, J = 8. 3 Hz), 8.00 (2H, d, J = 8.3 Hz).
MS (m / z): 248 [M] ^<+> .

Example-51
The same operation was carried out except that dichlorobis (triphenylphosphine) palladium (0.030 mmol, 21 mg) was used instead of dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium in Example-50, Formation of methyl 4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example-52
The same operation was performed except that the potassium acetate of Example-50 was 7.20 mmol (706 mg) and dimethyl sulfoxide (6.0 mL) was used instead of ethanol, and 4- (5,5-dimethyl-1, The formation of methyl 3,2-dioxaborinan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

  Example-53

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ安息香酸メチル（１．００ｍｍｏｌ，２１５ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、１，４−ブタンジオール（２．２０ｍｍｏｌ，１９８ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより４−（１，３，２−ジオキサボレパン−２−イル）安息香酸メチルの生成を確認した（ＮＭＲ収率：７５％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．９８（４Ｈ，ｂｒｓ），３．９２（３Ｈ，ｓ），４．２２（４Ｈ，ｂｒｓ），７．８７（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ），７．９８（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ）．
ＭＳ（ｍ／ｚ）：２３４［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. To this reaction solution, methyl 4-bromobenzoate (1.00 mmol, 215 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 1,4-butanediol (2.20 mmol, 198 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. ¹ H NMR confirmed the formation of methyl 4- (1,3,2-dioxabolep-2-yl) benzoate (NMR yield: 75%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.98 (4H, brs), 3.92 (3H, s), 4.22 (4H, brs), 7.87 (2H, d, J = 8. 4 Hz), 7.98 (2H, d, J = 8.4 Hz).
MS (m / z): 234 [M] ^<+> .

Example-54
In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichlorobis (triphenylphosphine) palladium (0.030 mmol, 21 mg), potassium acetate (7 20 mmol, 706 mg) was added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. To this reaction solution, methyl 4-bromobenzoate (1.00 mmol, 215 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 1,4-butanediol (2.20 mmol, 198 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. The formation of methyl 4- (1,3,2-dioxabolepan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 73%).

Example-55
Instead of 2,2′-bi (1,3,2-benzodioxaborol) in Example-13, 5,5′-di-tert-butyl-2,2′-bi (1,3, The same operation was performed except that 2-benzodioxaborol) (1.10 mmol, 385 mg) was used, and 4- (4,4,5,5-tetramethyl-1,3,2-) was observed by ¹ H NMR. Formation of methyl dioxaborolan-2-yl) benzoate was confirmed (NMR yield 90%).

  Example-56

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に１−ブロモ−４−ｔｅｒｔ−ブチルベンゼン（１．００ｍｍｏｌ，２１３ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、反応混合物に水を加え、ジエチルエーテルで抽出し、無水硫酸マグネシウムで乾燥した。それを濃縮し、さらにヘキサン抽出し、その溶液を濃縮することにより、白色固体の２−（４−ｔｅｒｔ−ブチルフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランを得た（２２３ｍｇ，収率８８％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３２（９Ｈ，ｓ），１．３３（１２Ｈ，ｓ），７．４０（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），７．７５（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 1-Bromo-4-tert-butylbenzene (1.00 mmol, 213 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, water was added to the reaction mixture, extracted with diethyl ether, and dried over anhydrous magnesium sulfate. It is concentrated, further extracted with hexane, and the solution is concentrated to give 2- (4-tert-butylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane as a white solid. (223 mg, 88% yield) was obtained.
¹ H-NMR (deuterated chloroform, ppm): δ1.32 (9H, s), 1.33 (12H, s), 7.40 (2H, d, J = 8.3 Hz), 7.75 (2H, d, J = 8.3 Hz).

Example-57
The same procedure as in Example 56 was performed except that the amount of potassium acetate in Example 56 was 3.00 mmol (294 mg) and ethanol (6.0 mL) was used instead of dimethyl sulfoxide, and 2- (4-tert-butylphenyl)- Formation of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 60%).

  Example-58

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ安息香酸エチル（１．００ｍｍｏｌ，２２９ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に酢酸エチルを加えろ過し、ろ液を濃縮した。水を加え、ジエチルエーテルで抽出し、ろ液を濃縮した。水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮することにより、白色固体の４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸エチルを得た（２５９ｍｇ，収率９４％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３６（１２Ｈ，ｓ），１．４０（３Ｈ，ｔ， Ｊ＝７．０Ｈｚ），４．３８（２Ｈ，ｑ，Ｊ＝７．０Ｈｚ），７．８６（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），８．０２（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. To this reaction solution, ethyl 4-bromobenzoate (1.00 mmol, 229 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, ethyl acetate was added to the reaction mixture and filtered, and the filtrate was concentrated. Water was added, extracted with diethyl ether, and the filtrate was concentrated. Water was added and extracted with hexane. The organic layer is dried over anhydrous magnesium sulfate, filtered, and the filtrate is concentrated to give 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) as a white solid. Ethyl benzoate was obtained (259 mg, 94% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.36 (12H, s), 1.40 (3H, t, J = 7.0 Hz), 4.38 (2H, q, J = 7.0 Hz), 7.86 (2H, d, J = 8.3 Hz), 8.02 (2H, d, J = 8.3 Hz).

Example-59
The same procedure was followed except that the potassium acetate of Example-58 was adjusted to 3.00 mmol (294 mg), and ethanol (6.0 mL) was used instead of dimethyl sulfoxide, and 4- (4,4,5,5- The production of ethyl tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

  Example-60

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に１−ブロモ−４−（トリフルオロメトキシ）ベンゼン（１．００ｍｍｏｌ，２４１ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に酢酸エチルを加えろ過し、ろ液を濃縮した。水を加え、ジエチルエーテルで抽出し、ろ液を濃縮した。水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮することにより、白色固体の４−トリフルオロメトキシ［１−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）］ベンゼンを得た（２２５ｍｇ，収率７８％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３４（１２Ｈ，ｓ），７．２０（２Ｈ，ｄ，Ｊ＝８．８Ｈｚ），７．８４（２Ｈ，ｄ，Ｊ＝８．８Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. To this reaction solution was added 1-bromo-4- (trifluoromethoxy) benzene (1.00 mmol, 241 mg), and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, ethyl acetate was added to the reaction mixture and filtered, and the filtrate was concentrated. Water was added, extracted with diethyl ether, and the filtrate was concentrated. Water was added and extracted with hexane. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated to give 4-trifluoromethoxy [1- (4,4,5,5-tetramethyl-1,3,2- Dioxaborolan-2-yl)] benzene was obtained (225 mg, 78% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.34 (12H, s), 7.20 (2H, d, J = 8.8 Hz), 7.84 (2H, d, J = 8.8 Hz).

Example-61
The same operation was carried out except that the potassium acetate of Example-60 was changed to 3.00 mmol (294 mg) and ethanol (6.0 mL) was used instead of dimethyl sulfoxide, and 4-trifluoromethoxy [1- (4, 4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)] benzene was confirmed by ¹ H NMR (NMR yield 81%).

  Example-62

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−（トリフルオロメチルチオ）ブロモベンゼン（１．００ｍｍｏｌ，２５７ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に酢酸エチルを加えろ過し、ろ液を濃縮した。水を加え、ジエチルエーテルで抽出し、ろ液を濃縮した。水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮することにより、白色固体の２−（４−トリフルオロメチルチオフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランを得た（２５８ｍｇ，収率８５％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３５（１２Ｈ，ｓ），７．６４（２Ｈ，ｄ， Ｊ＝８．３Ｈｚ），７．８４（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 4- (Trifluoromethylthio) bromobenzene (1.00 mmol, 257 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, ethyl acetate was added to the reaction mixture and filtered, and the filtrate was concentrated. Water was added, extracted with diethyl ether, and the filtrate was concentrated. Water was added and extracted with hexane. The organic layer is dried over anhydrous magnesium sulfate, filtered, and the filtrate is concentrated to give white solid 2- (4-trifluoromethylthiophenyl) -4,4,5,5-tetramethyl-1,3, 2-Dioxaborolane was obtained (258 mg, 85% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.35 (12H, s), 7.64 (2H, d, J = 8.3 Hz), 7.84 (2H, d, J = 8.3 Hz).

Example-63
The same procedure was followed except that the potassium acetate of Example-62 was changed to 7.2 mmol (706 mg) and dimethyl sulfoxide (6.0 mL) was used instead of ethanol, and 2- (4-trifluoromethylthiophenyl)- Formation of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 75%).

  Example-64

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に４−ブロモチオアニソール（１．００ｍｍｏｌ，２０３ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮した。得られた残渣を蒸留することにより、白色固体の２−（４−メチルチオフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランを得た（２４８ｍｇ，収率９９％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３３（１２Ｈ，ｓ），２．４９（３Ｈ，ｓ），δ７．２２（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），７．７０（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 4-Bromothioanisole (1.00 mmol, 203 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, water was added to the reaction mixture and extracted with hexane. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated. The obtained residue was distilled to obtain 2- (4-methylthiophenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (248 mg, yield 99%) as a white solid. ).
¹ H-NMR (deuterated chloroform, ppm): δ1.33 (12H, s), 2.49 (3H, s), δ7.22 (2H, d, J = 8.3 Hz), 7.70 (2H, d, J = 8.3 Hz).

Example-65
The same procedure was performed except that ethanol (6.0 mL) was used instead of dimethyl sulfoxide in an amount of 3.00 mmol (294 mg) of potassium acetate of Example-64, and 2- (4-methylthiophenyl) -4, Formation of 4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 40%).

  Example-66

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に３−ブロモアニリン（１．００ｍｍｏｌ，１７２ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に酢酸エチルを加えろ過し、ろ液を濃縮した。水を加え、ジエチルエーテルで抽出し、ろ液を濃縮した。水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮することにより、白色固体の４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）アニリンを得た（１６９ｍｇ，収率７７％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３３（１２Ｈ，ｓ），６．７９（１Ｈ，ｍ），７．１３（１Ｈ，ｓ），７．１７（１Ｈ，ｔ，Ｊ＝７．２Ｈｚ），７．２１（１Ｈ，ｄ，Ｊ＝７．２Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 3-Bromoaniline (1.00 mmol, 172 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, ethyl acetate was added to the reaction mixture and filtered, and the filtrate was concentrated. Water was added, extracted with diethyl ether, and the filtrate was concentrated. Water was added and extracted with hexane. The organic layer is dried over anhydrous magnesium sulfate, filtered, and the filtrate is concentrated to give 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) as a white solid. Aniline was obtained (169 mg, 77% yield).
¹ H-NMR (deuterated chloroform, ppm): δ1.33 (12H, s), 6.79 (1H, m), 7.13 (1H, s), 7.17 (1H, t, J = 7. 2 Hz), 7.21 (1H, d, J = 7.2 Hz).

Example-67
The same procedure was performed except that ethanol potassium (6.0 mL) was used instead of dimethyl sulfoxide in an amount of 3.00 mmol (294 mg) of potassium acetate in Example-66, and 4- (4, 4, 5, 5- The formation of tetramethyl-1,3,2-dioxaborolan-2-yl) aniline was confirmed by ¹ H NMR (NMR yield 85%).

  Example-68

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ−２−フルオロアニリン（１．００ｍｍｏｌ，１９０ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に酢酸エチルを加え、ろ過し、ろ液を濃縮した。ヘキサンで洗った後、水を加え、ジエチルエーテルで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮することにより、白色固体の２−フロオロ−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）アニリンを得た（１７５ｍｇ，収率７４％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３２（１２Ｈ，ｓ），３．９０（２Ｈ，ｓ），６．７４（１Ｈ，ｔ，Ｊ＝８．３Ｈｚ），７．３８（１Ｈ，ｄ，Ｊ＝４．８Ｈｚ），７．４０（１Ｈ，ｄ，Ｊ＝８．４Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 4-Bromo-2-fluoroaniline (1.00 mmol, 190 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, ethyl acetate was added to the reaction mixture, filtered, and the filtrate was concentrated. After washing with hexane, water was added and extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated to give 2-fluoro-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl) aniline was obtained (175 mg, 74% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.32 (12H, s), 3.90 (2H, s), 6.74 (1H, t, J = 8.3 Hz), 7.38 (1H, d, J = 4.8 Hz), 7.40 (1H, d, J = 8.4 Hz).

Example-69
The same operation was carried out except that the potassium acetate of Example-68 was adjusted to 3.00 mmol (294 mg) and ethanol (6.0 mL) was used instead of dimethyl sulfoxide, and 2-fluoro-4- (4, 4, The formation of 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline was confirmed by ¹ H NMR (NMR yield 60%).

  Example-70

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４’−ブロモアセトアニリド（１．００ｍｍｏｌ，２１４ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に酢酸エチルを加えろ過し、ろ液を濃縮した。ヘキサンで洗った後、水を加え、ジエチルエーテルで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮することにより、白色固体の４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）アセトアニリドを得た（１６８ｍｇ，収率６５％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３４（１２Ｈ，ｓ），２．１８（３Ｈ，ｓ），２．３６（１Ｈ，ｓ），７．５１（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），７．７６（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, 4′-bromoacetanilide (1.00 mmol, 214 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, ethyl acetate was added to the reaction mixture and filtered, and the filtrate was concentrated. After washing with hexane, water was added and extracted with diethyl ether. The organic layer is dried over anhydrous magnesium sulfate, filtered, and the filtrate is concentrated to give 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) as a white solid. Acetanilide was obtained (168 mg, yield 65%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.34 (12H, s), 2.18 (3H, s), 2.36 (1H, s), 7.51 (2H, d, J = 8. 3 Hz), 7.76 (2H, d, J = 8.3 Hz).

Example-71
The same procedure as in Example 70 was performed except that 7.2 mmol (706 mg) of potassium acetate was used and dimethyl sulfoxide (6.0 mL) was used instead of ethanol. 4- (4,4,5,5- The formation of tetramethyl-1,3,2-dioxaborolan-2-yl) acetanilide was confirmed by ¹ H NMR (NMR yield 75%).

  Example-72

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に４−ブロモベンジルアルコール（１．００ｍｍｏｌ，１８７ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に酢酸エチルを加えろ過し、ろ液を濃縮した。水を加え、ジエチルエーテルで抽出し、ろ液を濃縮した。水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮することにより、白色固体の４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンジルアルコールを得た（２３２ｍｇ，収率９９％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３５（１２Ｈ，ｓ），１．６８（１Ｈ，ｓ），４．７２（２Ｈ，ｄ，Ｊ＝５．１Ｈｚ），７．３７（２Ｈ，ｄ，Ｊ＝７．８Ｈｚ），７．８１（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 4-Bromobenzyl alcohol (1.00 mmol, 187 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, ethyl acetate was added to the reaction mixture and filtered, and the filtrate was concentrated. Water was added, extracted with diethyl ether, and the filtrate was concentrated. Water was added and extracted with hexane. The organic layer is dried over anhydrous magnesium sulfate, filtered, and the filtrate is concentrated to give 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) as a white solid. Benzyl alcohol was obtained (232 mg, 99% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.35 (12H, s), 1.68 (1H, s), 4.72 (2H, d, J = 5.1 Hz), 7.37 (2H, d, J = 7.8 Hz), 7.81 (2H, d, J = 8.3 Hz).

Example-73
The same procedure was followed except that the potassium acetate of Example-72 was made 3.00 mmol (294 mg) and ethanol (6.0 mL) was used instead of dimethyl sulfoxide, and 4- (4,4,5,5- The formation of tetramethyl-1,3,2-dioxaborolan-2-yl) benzyl alcohol was confirmed by ¹ H NMR (NMR yield 76%).

  Example-74

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に４−ブロモベンズアミド（１．００ｍｍｏｌ，２００ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。その溶液を濃縮し、得られた残渣を蒸留することにより、白色固体の４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンズアミドを得た（１７８ｍｇ，収率７２％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３５（１２Ｈ，ｓ），７．８０（２Ｈ，ｄ，Ｊ＝７．３Ｈｚ），７．８８（２Ｈ，ｄ，Ｊ＝７．３Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 4-Bromobenzamide (1.00 mmol, 200 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. The solution was concentrated and the resulting residue was distilled to obtain 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzamide as a white solid ( 178 mg, 72% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.35 (12H, s), 7.80 (2H, d, J = 7.3 Hz), 7.88 (2H, d, J = 7.3 Hz).

Example-75
The same procedure was performed except that ethanol potassium (6.0 mL) was used instead of dimethyl sulfoxide in an amount of 3.00 mmol (294 mg) of potassium acetate in Example-74, and 4- (4, 4, 5, 5- The formation of tetramethyl-1,3,2-dioxaborolan-2-yl) benzamide was confirmed by ¹ H NMR (NMR yield 90%).

  Example-76

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ安息香酸（１．００ｍｍｏｌ，２０１ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、残渣をジエチルエーテル抽出し、ろ過、ろ液を濃縮し、ヘキサンで抽出した。その溶液を濃縮し、得られた残渣を蒸留することにより、白色固体の４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸を得た（１４９ｍｇ，収率６０％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３６（１２Ｈ，ｓ），７．９０（２Ｈ，ｄ， Ｊ＝８．３Ｈｚ），８．０８（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）．
ＩＲ：１６８３ｃｍ^−１。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 4-Bromobenzoic acid (1.00 mmol, 201 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, the residue was extracted with diethyl ether, filtered, and the filtrate was concentrated and extracted with hexane. The solution was concentrated, and the resulting residue was distilled to obtain 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoic acid as a white solid. (149 mg, 60% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.36 (12H, s), 7.90 (2H, d, J = 8.3 Hz), 8.08 (2H, d, J = 8.3 Hz).
IR: 1683 cm < ^-1 >.

  Example-77

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモベンズスルホニルフルオリド（１．００ｍｍｏｌ，２３９ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、ヘキサンで抽出した。その溶液を濃縮することにより、白色固体の４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンスルホニルフルオリドを得た（２６０ｍｇ，収率９１％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３７（１２Ｈ，ｓ），７．９９（３Ｈ，ｄ， Ｊ＝８．３Ｈｚ），８．０４（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）．
^１９Ｆ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ−６６（１Ｆ，ｓ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 4-Bromobenzsulfonyl fluoride (1.00 mmol, 239 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, the mixture was extracted with hexane. The solution was concentrated to obtain white solid 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzenesulfonyl fluoride (260 mg, yield 91). %).
¹ H-NMR (deuterated chloroform, ppm): δ 1.37 (12H, s), 7.9 (3H, d, J = 8.3 Hz), 8.04 (2H, d, J = 8.3 Hz).
¹⁹ F-NMR (deuterated chloroform, ppm): δ-66 (1F, s).

Example-78
The same procedure was followed except that the potassium acetate of Example-77 was adjusted to 7.2 mmol (706 mg) and dimethyl sulfoxide (6.0 mL) was used instead of ethanol, and 4- (4,4,5,5- The formation of tetramethyl-1,3,2-dioxaborolan-2-yl) benzenesulfonyl fluoride was confirmed by ¹ H NMR (NMR yield 20%).

  Example-79

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモベンゼンスルホン酸ペンタフルオロフェニルエステル（１．００ｍｍｏｌ，４０３ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、トルエンで抽出し、ろ過し、ろ液を濃縮、ヘキサンで抽出した。その溶液を濃縮することにより、白色固体の４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンスルホン酸 ペンタフルオロフェニルを得た（３５１ｍｇ，収率７８％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３８（１２Ｈ，ｓ），７．９５（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ），８．０２（２Ｈ，ｄ，Ｊ＝８．６Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 4-Bromobenzenesulfonic acid pentafluorophenyl ester (1.00 mmol, 403 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, extraction with toluene and filtration were performed, and the filtrate was concentrated and extracted with hexane. The solution was concentrated to obtain pentafluorophenyl (351 mg, yield of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzenesulfonate as a white solid. 78%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.38 (12H, s), 7.95 (2H, d, J = 8.5 Hz), 8.02 (2H, d, J = 8.6 Hz).

  Example-80

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモベンゼンスルホンアミド（１．００ｍｍｏｌ，２３６ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、残渣をジエチルエーテル抽出し、ろ過、ろ液を濃縮し、ヘキサンで抽出した。その溶液を濃縮し、得られた残渣を蒸留することにより、白色固体の４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゼンスルホンアミドを得た（１７０ｍｇ，収率６０％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３６（１２Ｈ，ｓ），４．７５（２Ｈ，ｓ），７．９１（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），７．９５（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 4-Bromobenzenesulfonamide (1.00 mmol, 236 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, the residue was extracted with diethyl ether, filtered, and the filtrate was concentrated and extracted with hexane. The solution was concentrated, and the resulting residue was distilled to obtain 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzenesulfonamide as a white solid. (170 mg, 60% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.36 (12H, s), 4.75 (2H, s), 7.91 (2H, d, J = 8.3 Hz), 7.95 (2H, d, J = 8.4 Hz).

Example-81
The same operation was performed except that the potassium acetate of Example-80 was 7.2 mmol (706 mg) and dimethyl sulfoxide (6.0 mL) was used instead of ethanol, and 4- (4,4,5,5- The formation of tetramethyl-1,3,2-dioxaborolan-2-yl) benzenesulfonamide was confirmed by ¹ H NMR (NMR yield 45%).

  Example-82

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に２−ブロモクロロベンゼン（１．００ｍｍｏｌ，１９１ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、残渣をジエチルエーテル抽出し、ろ過、ろ液を濃縮した。その得られた残渣を蒸留することにより、白色固体の２−（２−クロロフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランを得た（１３４ｍｇ，収率５６％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３７（１２Ｈ，ｓ），７．２０−７．２４（１Ｈ，ｍ），７．３３−７．３４（２Ｈ，ｍ），７．６８（１Ｈ，ｄ，Ｊ＝７．４Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 2-Bromochlorobenzene (1.00 mmol, 191 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, the residue was extracted with diethyl ether, filtered, and the filtrate was concentrated. The obtained residue was distilled to obtain 2- (2-chlorophenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (134 mg, yield 56%) as a white solid. ).
¹ H-NMR (deuterated chloroform, ppm): δ 1.37 (12H, s), 7.20-7.24 (1H, m), 7.33-7.34 (2H, m), 7.68 ( 1H, d, J = 7.4 Hz).

Example-83
The same procedure was performed except that ethanol (6.0 mL) was used instead of dimethyl sulfoxide in an amount of 3.00 mmol (294 mg) of potassium acetate in Example-82, and 2- (2-chlorophenyl) -4,4 , 5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 70%).

  Example-84

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に２−ブロモベンゾトリフルオリド（１．００ｍｍｏｌ，２２５ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、反応混合物に水を加え、ジエチルエーテルで抽出し、無水硫酸マグネシウムで乾燥した。その溶液を濃縮し、さらにヘキサンで抽出し、濃縮することにより、白色固体の４，４，５，５−テトラメチル−２−（４−トリフルオロメチルフェニル）−１，３，２−ジオキサボロランを得た（１２０ｍｇ，収率４４％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３７（１２Ｈ，ｓ），７．４９−７．５１（２Ｈ，ｍ），７．６５−７．６７（１Ｈ，ｍ），７．７１−７．７３（１Ｈ，ｍ）．
ＭＳ（ｍ／ｚ）：２７２［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 2-Bromobenzotrifluoride (1.00 mmol, 225 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, water was added to the reaction mixture, extracted with diethyl ether, and dried over anhydrous magnesium sulfate. The solution was concentrated, further extracted with hexane, and concentrated to obtain 4,4,5,5-tetramethyl-2- (4-trifluoromethylphenyl) -1,3,2-dioxaborolane as a white solid. Obtained (120 mg, 44% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.37 (12H, s), 7.49-7.51 (2H, m), 7.65-7.67 (1H, m), 7.71- 7.73 (1H, m).
MS (m / z): 272 [M] ^<+> .

Example-85
The same operation was carried out except that the potassium acetate of Example-84 was 3.00 mmol (294 mg) and ethanol (6.0 mL) was used instead of dimethyl sulfoxide, and 4,4,5,5-tetramethyl- Formation of 2- (4-trifluoromethylphenyl) -1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 50%).

  Example-86

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に２−ブロモアセトフェノン（１．００ｍｍｏｌ，１９９ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）アセトフェノンの生成を確認した（ＮＭＲ収率３０％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．４４（１２Ｈ，ｓ），２．６１（３Ｈ，ｓ），７．４１−７．４５（１Ｈ，ｍ），７．５１−７．５６（２Ｈ，ｍ），７．８２（２Ｈ，ｄ，Ｊ＝８．６Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 2-Bromoacetophenone (1.00 mmol, 199 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. The formation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) acetophenone was confirmed by ¹ H NMR (NMR yield 30%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.44 (12H, s), 2.61 (3H, s), 7.41-7.45 (1H, m), 7.51-7.56 ( 2H, m), 7.82 (2H, d, J = 8.6 Hz).

Example-87
The same operation was performed except that ethanol potassium (6.0 mL) was used instead of dimethyl sulfoxide in an amount of 3.00 mmol (294 mg) of potassium acetate of Example-86, and 2- (4,4,5,5- The formation of tetramethyl-1,3,2-dioxaborolan-2-yl) acetophenone was confirmed by ¹ H NMR (NMR yield 80%).

  Example-88

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に２−ブロモ安息香酸メチル（１．００ｍｍｏｌ，２１５ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルの生成を確認した（ＮＭＲ収率８０％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．４２（１２Ｈ，ｓ），３．９１（３Ｈ，ｓ），７．３９−７．４３（１Ｈ，ｍ），７．４９−７．５２（２Ｈ，ｍ），７．９４（１Ｈ，ｄ，Ｊ＝７．６Ｈｚ）．
ＭＳ（ｍ／ｚ）：２４７［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, methyl 2-bromobenzoate (1.00 mmol, 215 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. Formation of methyl 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 80%).
¹ H-NMR (deuterated chloroform, ppm): δ1.42 (12H, s), 3.91 (3H, s), 7.39-7.43 (1H, m), 7.49-7.52 ( 2H, m), 7.94 (1H, d, J = 7.6 Hz).
MS (m / z): 247 [M] ^<+> .

  Example-89

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に２，４，５−トリメチルブロモベンゼン（１．００ｍｍｏｌ，１９９ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、反応混合物に水を加え、ジエチルエーテルで抽出した。その有機層をろ過し、ろ液を濃縮し、得られた残渣を蒸留することにより、白色固体の２−（２，４，５−トリメチルフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランを得た（２０７ｍｇ，収率８４％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３３（１２Ｈ，ｓ），２．２２（３Ｈ，ｓ），２．２３（３Ｈ，ｓ），２．４７（３Ｈ，ｓ），６．９５（１Ｈ，ｓ），７．５２（１Ｈ，ｓ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 2,4,5-Trimethylbromobenzene (1.00 mmol, 199 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, water was added to the reaction mixture, and the mixture was extracted with diethyl ether. The organic layer was filtered, the filtrate was concentrated, and the resulting residue was distilled to give 2- (2,4,5-trimethylphenyl) -4,4,5,5-tetramethyl- 1,3,2-dioxaborolane was obtained (207 mg, 84% yield).
¹ H-NMR (deuterated chloroform, ppm): δ1.33 (12H, s), 2.22 (3H, s), 2.23 (3H, s), 2.47 (3H, s), 6.95 (1H, s), 7.52 (1H, s).

Example-90
The same procedure was performed except that ethanol (6.0 mL) was used instead of dimethyl sulfoxide in an amount of 3.00 mmol (294 mg) of potassium acetate of Example-89, and 2- (2,4,5-trimethylphenyl) was obtained. ) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 50%).

  Example-91

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に２−ブロモ−１，３−ジメチルベンゼン（１．００ｍｍｏｌ，１８５ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。さらにトルエンおよび蒸留水を適量添加し、１４時間反応させた。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、反応混合物に水を加え、ジエチルエーテルで抽出した。その有機層をろ過し、ろ液を濃縮し、得られた残渣を蒸留することにより、無色液体の２−（２，６−ジメチルフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランを得た（１１１ｍｇ，収率４８％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３８（１２Ｈ，ｓ），２．３９（６Ｈ，ｓ），δ６．９４（２Ｈ，ｄ，Ｊ＝７．３Ｈｚ）， ７．１２（１Ｈ，ｔ，Ｊ＝７．３Ｈｚ）．
ＭＳ（ｍ／ｚ）：２３２［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 2-Bromo-1,3-dimethylbenzene (1.00 mmol, 185 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. Further, appropriate amounts of toluene and distilled water were added and reacted for 14 hours. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, water was added to the reaction mixture, and the mixture was extracted with diethyl ether. The organic layer was filtered, the filtrate was concentrated, and the resulting residue was distilled to give 2- (2,6-dimethylphenyl) -4,4,5,5-tetramethyl-1, 3,2-dioxaborolane was obtained (111 mg, 48% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.38 (12H, s), 2.39 (6H, s), δ 6.94 (2H, d, J = 7.3 Hz), 7.12 (1H, t, J = 7.3 Hz).
MS (m / z): 232 [M] ^<+> .

Example-92
The same procedure as in Example 91 was performed except that 3.00 mmol (294 mg) of potassium acetate was used and ethanol (6.0 mL) was used instead of dimethyl sulfoxide. 2- (2,6-dimethylphenyl)- Formation of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 30%).

  Example-93

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に２−ブロモ−５−フルオロベンゾニトリル（１．００ｍｍｏｌ，２００ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより５−フルオロ−２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゾニトリルの生成を確認した（ＮＭＲ収率：４５％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３８（１２Ｈ，ｓ）， ７．３９−７．４２（２Ｈ，ｍ）， ７．９０（１Ｈ，ｔ，Ｊ＝７．３Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 2-Bromo-5-fluorobenzonitrile (1.00 mmol, 200 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. Formation of 5-fluoro-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzonitrile was confirmed by ¹ H NMR (NMR yield: 45%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.38 (12H, s), 7.39-7.42 (2H, m), 7.90 (1H, t, J = 7.3 Hz).

  Example-94

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に１−ブロモ−３，４，５−トリフルオロベンゼン（１．００ｍｍｏｌ，２１１ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に酢酸エチルを加えろ過し、ろ液を濃縮した。水を加え、ジエチルエーテルで抽出し、ろ液を濃縮した。水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮することにより、白色固体の２−（３，４，５−トリフルオロフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランを得た（２５５ｍｇ，収率９９％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３３（１２Ｈ，ｓ），７．３８（２Ｈ，ｔ， Ｊ＝７．４Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, 1-bromo-3,4,5-trifluorobenzene (1.00 mmol, 211 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, ethyl acetate was added to the reaction mixture and filtered, and the filtrate was concentrated. Water was added, extracted with diethyl ether, and the filtrate was concentrated. Water was added and extracted with hexane. The organic layer is dried over anhydrous magnesium sulfate, filtered, and the filtrate is concentrated to give 2- (3,4,5-trifluorophenyl) -4,4,5,5-tetramethyl-1 as a white solid. , 3,2-dioxaborolane was obtained (255 mg, 99% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.33 (12H, s), 7.38 (2H, t, J = 7.4 Hz).

Example-95
The same procedure as in Example 94 was performed except that 7.2 mmol (706 mg) of potassium acetate was used and dimethyl sulfoxide (6.0 mL) was used instead of ethanol. 2- (3,4,5-trifluoro Formation of (phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 99%).

  Example-96

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に１−ブロモ−３，４−ジフルオロベンゼン（１．００ｍｍｏｌ，１９３ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、反応混合物に水を加え、ジエチルエーテルで抽出した。その有機層をろ過し、ろ液を濃縮し、得られた残渣を蒸留することにより、無色液体の２−（３，４−ジフルオロフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランを得た（１５１ｍｇ，収率６３％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３３（１２Ｈ，ｓ），７．１４（１Ｈ，ｄ， Ｊ＝１０．７Ｈｚ），７．５２（１Ｈ，ｔ，Ｊ＝６．５Ｈｚ），７．５８（１Ｈ，ｔ，Ｊ＝９．６Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. To this reaction solution was added 1-bromo-3,4-difluorobenzene (1.00 mmol, 193 mg), and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, water was added to the reaction mixture, and the mixture was extracted with diethyl ether. The organic layer was filtered, the filtrate was concentrated, and the resulting residue was distilled to give colorless liquid 2- (3,4-difluorophenyl) -4,4,5,5-tetramethyl-1, 3,2-dioxaborolane was obtained (151 mg, 63% yield).
¹ H-NMR (deuterated chloroform, ppm): δ1.33 (12H, s), 7.14 (1H, d, J = 10.7 Hz), 7.52 (1H, t, J = 6.5 Hz), 7.58 (1H, t, J = 9.6 Hz).

Example-97
The same procedure was performed except that ethanol (6.0 mL) was used instead of dimethyl sulfoxide in an amount of 3.00 mmol (294 mg) of potassium acetate in Example-96, and 2- (3,4-difluorophenyl)- Formation of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 80%).

  Example-98

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に１−ブロモ−３，５−ビス（トリフルオロメチル）ベンゼン（１．００ｍｍｏｌ，２９３ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に酢酸エチルを加えろ過し、ろ液を濃縮した。水を加え、ジエチルエーテルで抽出し、ろ液を濃縮した。水を加え、ヘキサンで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮することにより、白色固体の２−［３，５−ビス（トリフルオロメチル）フェニル］−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランを得た（３１３ｍｇ，収率９２％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３７（１２Ｈ，ｓ），７．９４（１Ｈ，ｓ），８．２３（２Ｈ，ｓ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, 1-bromo-3,5-bis (trifluoromethyl) benzene (1.00 mmol, 293 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, ethyl acetate was added to the reaction mixture and filtered, and the filtrate was concentrated. Water was added, extracted with diethyl ether, and the filtrate was concentrated. Water was added and extracted with hexane. The organic layer is dried over anhydrous magnesium sulfate, filtered, and the filtrate is concentrated to give 2- [3,5-bis (trifluoromethyl) phenyl] -4,4,5,5-tetramethyl as a white solid. -1,3,2-dioxaborolane was obtained (313 mg, 92% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.37 (12H, s), 7.94 (1H, s), 8.23 (2H, s).

Example-99
The same procedure as in Example 98 was performed except that 7.2 mmol (706 mg) of potassium acetate was used and dimethyl sulfoxide (6.0 mL) was used instead of ethanol. 2- [3,5-bis (trifluoro) Methyl) phenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 99%).

  Example-100

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に５−ブロモ−１，３−ベンゾジオキソール（１．００ｍｍｏｌ，２０１ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、反応混合物に水を加え、ジエチルエーテルで抽出した。その得られた有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮し、ヘキサンで抽出した。その溶液を濃縮することにより、無色液体の５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）−１，３−ベンゾジオキソールを得た（２４１ｍｇ，収率９７％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３２（１２Ｈ，ｓ），５．９５（２Ｈ，ｓ），６．８３（１Ｈ，ｄ，Ｊ＝７．９Ｈｚ），７．２４（１Ｈ，ｓ）， ７．３６（１Ｈ，ｄ，Ｊ＝１．１，７．９Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. To this reaction solution, 5-bromo-1,3-benzodioxole (1.00 mmol, 201 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, water was added to the reaction mixture, and the mixture was extracted with diethyl ether. The obtained organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated and extracted with hexane. The solution was concentrated to obtain colorless liquid 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-benzodioxole ( 241 mg, yield 97%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.32 (12H, s), 5.95 (2H, s), 6.83 (1H, d, J = 7.9 Hz), 7.24 (1H, s), 7.36 (1H, d, J = 1.1, 7.9 Hz).

Example-101
The same operation was carried out except that ethanol potassium (6.0 mL) was used instead of dimethyl sulfoxide in an amount of 3.00 mmol (294 mg) of potassium acetate of Example-100, and 5- (4, 4, 5, 5- Formation of tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-benzodioxole was confirmed by ¹ H NMR (NMR yield 60%).

  Example-102

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ−２−フルオロベンズアルデヒド（１．００ｍｍｏｌ，２０３ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより２−フルオロ−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンズアルデヒドの生成を^１Ｈ ＮＭＲで確認した（ＮＭＲ収率５５％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３６（１２Ｈ，ｓ），７．５９（１Ｈ，ｄ， Ｊ＝１０．２Ｈｚ），７．６７（１Ｈ，ｄ，Ｊ＝７．６Ｈｚ），７．８５（１Ｈ，ｔ，Ｊ＝７．１Ｈｚ）， １０．４０（１Ｈ，ｓ）．
ＭＳ（ｍ／ｚ）：２５０［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 4-Bromo-2-fluorobenzaldehyde (1.00 mmol, 203 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. The ¹ H NMR confirmed the formation of 2-fluoro-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzaldehyde in ¹ H NMR (NMR yield: 55% ).
¹ H-NMR (deuterated chloroform, ppm): δ 1.36 (12H, s), 7.59 (1H, d, J = 10.2 Hz), 7.67 (1H, d, J = 7.6 Hz), 7.85 (1H, t, J = 7.1 Hz), 10.40 (1H, s).
MS (m / z): 250 [M] ^<+> .

Example-103
The same procedure was carried out except that the potassium acetate of Example-102 was adjusted to 3.00 mmol (294 mg), and ethanol (6.0 mL) was used instead of dimethyl sulfoxide, and 2-fluoro-4- (4, 4, The formation of 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzaldehyde was confirmed by ¹ H NMR (NMR yield 60%).

  Example-104

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に４−ヨード安息香酸メチル（１．００ｍｍｏｌ，２６２ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルの生成を^１Ｈ ＮＭＲで確認した（ＮＭＲ収率９９％）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. To this reaction solution, methyl 4-iodobenzoate (1.00 mmol, 262 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. The ¹ H NMR 4-production of (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR 99% yield).

Example-105
The same operation was performed except that ethanol potassium (6.0 mL) was used instead of dimethyl sulfoxide in an amount of 3.00 mmol (294 mg) of potassium acetate in Example 104, and 4- (4, 4, 5, 5- The formation of tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate methyl was confirmed by ¹ H NMR (NMR yield 85%).

  Example-106

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液にトリフルオロメタンスルホン酸 ４−メトキシフェニル（１．００ｍｍｏｌ，２５６ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより４−メトキシフェニル−２−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランの生成を^１Ｈ ＮＭＲで確認した（ＮＭＲ収率９９％）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. To this reaction solution, 4-methoxyphenyl trifluoromethanesulfonate (1.00 mmol, 256 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. ^The formation of 4-methoxyphenyl-2-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR by ¹ H NMR (99% yield of NMR).

Example-107
The same procedure was carried out except that the potassium acetate of Example-106 was adjusted to 3.00 mmol (294 mg) and ethanol (6.0 mL) was used instead of dimethyl sulfoxide, and 4-methoxyphenyl-2-4,4, Formation of 5,5-tetramethyl-1,3,2-dioxaborolane was confirmed by ¹ H NMR (NMR yield 15%).

  Example-108

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモベンジルアミン塩酸塩（１．００ｍｍｏｌ，２２３ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，２−ジメチル−１，３−プロパンジオール（２．２０ｍｍｏｌ，２２９ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、反応混合物に酢酸エチルを加えろ過し、ろ液を濃縮した。ヘキサンで洗った後、水を加え、ジエチルエーテルで抽出した。有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮した。得られた残渣を蒸留することにより、白色固体の４−（５，５−ジメチル−１，３，２−ジオキサボリナン−２−イル）ベンジルアミンを得た（１２７ｍｇ，収率５８％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．０１（１２Ｈ，ｓ），１．９０（２Ｈ，ｓ），３．７５（３Ｈ，ｓ），３．９２（２Ｈ，ｂｒｓ），７．３３（２Ｈ，ｄ，Ｊ＝６．８Ｈｚ），７．７８（２Ｈ，ｄ，Ｊ＝６．８Ｈｚ）．
ＭＳ（ｍ／ｚ）：２３２［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 4-Bromobenzylamine hydrochloride (1.00 mmol, 223 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,2-dimethyl-1,3-propanediol (2.20 mmol, 229 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, ethyl acetate was added to the reaction mixture and filtered, and the filtrate was concentrated. After washing with hexane, water was added and extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated. The obtained residue was distilled to obtain 4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) benzylamine as a white solid (127 mg, yield 58%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.01 (12H, s), 1.90 (2H, s), 3.75 (3H, s), 3.92 (2H, brs), 7.33 (2H, d, J = 6.8 Hz), 7.78 (2H, d, J = 6.8 Hz).
MS (m / z): 232 [M] ^<+> .

Example-109
Except that the potassium acetate of Example-108 was 7.2 mmol (706 mg) and dimethyl sulfoxide (6.0 mL) was used instead of ethanol, the same operation was performed, and 4- (5,5-dimethyl-1, The formation of 3,2-dioxaborinan-2-yl) benzylamine was confirmed by ¹ H NMR (NMR yield 30%).

  Example-110

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に３−ブロモ−４−フルオロトルエン（１．００ｍｍｏｌ，１８９ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，２−ジメチル−１，３−プロパンジオール（２．２０ｍｍｏｌ，２２９ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより２−（２−フルオロ−５−メチルフェニル）−５，５−ジメチル−１，３，２−ジオキサボリナンの生成を確認した（ＮＭＲ収率８０％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．０３（６Ｈ，ｓ），３．７９（４Ｈ，ｓ），２．３０（３Ｈ，ｓ），６．９９（１Ｈ，ｔ，Ｊ＝８．６Ｈｚ），７．１４−７．１９（１Ｈ，ｍ），７．５０（１Ｈ，ｓ）．
ＭＳ（ｍ／ｚ）：２２２［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. To this reaction solution, 3-bromo-4-fluorotoluene (1.00 mmol, 189 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,2-dimethyl-1,3-propanediol (2.20 mmol, 229 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. The production of 2- (2-fluoro-5-methylphenyl) -5,5-dimethyl-1,3,2-dioxaborinane was confirmed by ¹ H NMR (NMR yield 80%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.03 (6H, s), 3.79 (4H, s), 2.30 (3H, s), 6.99 (1H, t, J = 8. 6 Hz), 7.14-7.19 (1 H, m), 7.50 (1 H, s).
MS (m / z): 222 [M] ^&lt; ^{+ &gt};.

Example-111
The same procedure was performed except that ethanol (6.0 mL) was used instead of dimethyl sulfoxide in an amount of 3.00 mmol (294 mg) of potassium acetate of Example-110, and 2- (2-fluoro-5-methylphenyl) was obtained. ) -5,5-dimethyl-1,3,2-dioxaborinane was confirmed by ¹ H NMR (NMR yield 50%).

  Example-112

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に２−ブロモベンゾトリフルオリド（１．００ｍｍｏｌ，２２５ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，２−ジメチル−１，３−プロパンジオール（２．２０ｍｍｏｌ，２２９ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、反応混合物に水を加え、ジエチルエーテルで抽出した。その得られた有機層を無水硫酸マグネシウムで乾燥後、ろ過し、ろ液を濃縮し、ヘキサンで抽出した。その溶液を濃縮することにより、白色固体の５，５−ジメチル−２−（トリフルオロメチルフェニル）−１，３，２−ジオキサボリナンを得た（１１９ｍｇ，収率４６％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．０６（６Ｈ，ｓ），３．７８（４Ｈ，ｓ），７．４４−７．４９（２Ｈ，ｍ），７．６２−７．６９（２Ｈ，ｍ）．
ＭＳ（ｍ／ｚ）：２７２［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 2-Bromobenzotrifluoride (1.00 mmol, 225 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,2-dimethyl-1,3-propanediol (2.20 mmol, 229 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, water was added to the reaction mixture, and the mixture was extracted with diethyl ether. The obtained organic layer was dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated and extracted with hexane. By concentrating the solution, white solid 5,5-dimethyl-2- (trifluoromethylphenyl) -1,3,2-dioxaborinane was obtained (119 mg, 46% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.06 (6H, s), 3.78 (4H, s), 7.44-7.49 (2H, m), 7.62-7.69 ( 2H, m).
MS (m / z): 272 [M] ^<+> .

  Example-113

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に２−ブロモ−１，３−ジメチルベンゼン（１．００ｍｍｏｌ，１８５ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，２−ジメチル−１，３−プロパンジオール（２．２０ｍｍｏｌ，２２９ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより２−（２，６−ジメチルフェニル）−５，５−ジメチル−１，３，２−ジオキサボリナンの生成を確認した（ＮＭＲ収率７０％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．１０ （６Ｈ，ｓ），２．３８（６Ｈ，ｓ），３．７９（４Ｈ，ｓ）， ６．９３ （２Ｈ，ｄ，Ｊ＝７．５Ｈｚ），７．０９（１Ｈ，ｔ，Ｊ＝７．５Ｈｚ）．
ＭＳ（ｍ／ｚ）：２１８［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 2-Bromo-1,3-dimethylbenzene (1.00 mmol, 185 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,2-dimethyl-1,3-propanediol (2.20 mmol, 229 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. The formation of 2- (2,6-dimethylphenyl) -5,5-dimethyl-1,3,2-dioxaborinane was confirmed by ¹ H NMR (NMR yield 70%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.10 (6H, s), 2.38 (6H, s), 3.79 (4H, s), 6.93 (2H, d, J = 7. 5 Hz), 7.09 (1H, t, J = 7.5 Hz).
MS (m / z): 218 [M] ^<+> .

  Example-114

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に１−ブロモ−４−エトキシ−２，３−ジフルオロベンゼン（１．００ｍｍｏｌ，２３７ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，２−ジメチル−１，３−プロパンジオール（２．２０ｍｍｏｌ，２２９ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、反応混合物に水を加え、ジエチルエーテルで抽出した。その有機層をろ過し、ろ液を濃縮し、得られた残渣を蒸留することにより、無色液体の２−（４−エトキシ−２，３−ジフルオロフェニル）−５，５−ジメチル−１，３，２ジオキサボリナンを得た（１０５ｍｇ，収率３９％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．０３（６Ｈ，ｓ），１．４５（３Ｈ，ｔ，Ｊ＝７．０Ｈｚ），３．７７（４Ｈ，ｓ），４．１３（２Ｈ，ｑ，Ｊ＝７．０Ｈｚ），６．６９（１Ｈ，ｔ，Ｊ＝７．６Ｈｚ），７．３６（１Ｈ，ｔ，Ｊ＝７．６Ｈｚ）．
ＭＳ（ｍ／ｚ）：２７０［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 1-Bromo-4-ethoxy-2,3-difluorobenzene (1.00 mmol, 237 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,2-dimethyl-1,3-propanediol (2.20 mmol, 229 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, water was added to the reaction mixture, and the mixture was extracted with diethyl ether. The organic layer was filtered, the filtrate was concentrated, and the resulting residue was distilled to give 2- (4-ethoxy-2,3-difluorophenyl) -5,5-dimethyl-1,3 as a colorless liquid. , 2 Dioxaborinane was obtained (105 mg, 39% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.03 (6H, s), 1.45 (3H, t, J = 7.0 Hz), 3.77 (4H, s), 4.13 (2H, q, J = 7.0 Hz), 6.69 (1H, t, J = 7.6 Hz), 7.36 (1H, t, J = 7.6 Hz).
MS (m / z): 270 [M] ^<+> .

  Example-115

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ安息香酸（１．００ｍｍｏｌ，２０１ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，２−ジメチル−１，３−プロパンジオール（２．２０ｍｍｏｌ，２２９ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより４−（５，５−ジメチル−１，３，２−ジオキサボリナン−２−イル）安息香酸の生成を確認した（ＮＭＲ収率６０％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．０３（６Ｈ，ｓ）， ３．７８（４Ｈ，ｓ），７．８５（２Ｈ，ｄ，Ｊ＝５．９Ｈｚ），８．００（２Ｈ，ｄ，Ｊ＝５．９Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 4-Bromobenzoic acid (1.00 mmol, 201 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,2-dimethyl-1,3-propanediol (2.20 mmol, 229 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. Formation of 4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) benzoic acid was confirmed by ¹ H NMR (NMR yield 60%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.03 (6H, s), 3.78 (4H, s), 7.85 (2H, d, J = 5.9 Hz), 8.00 (2H, d, J = 5.9 Hz).

  Example-116

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモベンズアミド（１．００ｍｍｏｌ，２００ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，２−ジメチル−１，３−プロパンジオール（２．２０ｍｍｏｌ，２２９ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより４−（５，５−ジメチル−１，３，２−ジオキサボリナン−２−イル）ベンズアミドの生成を確認した（ＮＭＲ収率９２％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．０３（６Ｈ，ｓ），３．７８（４Ｈ，ｓ），７．７７（２Ｈ，ｄ，Ｊ＝７．７Ｈｚ），７．８７（２Ｈ，ｄ，Ｊ＝８．２Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 4-Bromobenzamide (1.00 mmol, 200 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,2-dimethyl-1,3-propanediol (2.20 mmol, 229 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. ¹ H NMR confirmed the formation of 4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) benzamide (NMR yield 92%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.03 (6H, s), 3.78 (4H, s), 7.77 (2H, d, J = 7.7 Hz), 7.87 (2H, d, J = 8.2 Hz).

  Example-117

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に２−ブロモ安息香酸メチル（１．００ｍｍｏｌ，２１５ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，２−ジメチル−１，３−プロパンジオール（２．２０ｍｍｏｌ，２２９ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより２−（５，５−ジメチル−１，３，２−ジオキサボリナン−２−イル）安息香酸メチルの生成を確認した（ＮＭＲ収率６６％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．１１（６Ｈ，ｓ），３．８０（４Ｈ，ｓ），３．９２（３Ｈ，ｓ），７．３６−７．４０（１Ｈ，ｍ）， ７．４９−７．５２（２Ｈ，ｍ）， ７．９２（１Ｈ，ｔ，Ｊ＝７．３Ｈｚ）．
ＭＳ（ｍ／ｚ）：２４８［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, methyl 2-bromobenzoate (1.00 mmol, 215 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,2-dimethyl-1,3-propanediol (2.20 mmol, 229 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. The formation of methyl 2- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 66%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.11 (6H, s), 3.80 (4H, s), 3.92 (3H, s), 7.36-7.40 (1H, m) 7.49-7.52 (2H, m), 7.92 (1H, t, J = 7.3 Hz).
MS (m / z): 248 [M] ^<+> .

  Example-118

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に２−ブロモ安息香酸エチル（１．００ｍｍｏｌ，２２９ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，２−ジメチル−１，３−プロパンジオール（２．２０ｍｍｏｌ，２２９ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、ヘキサン抽出した。その溶液をろ過し、ろ液を濃縮し、得られた残渣を蒸留することにより、白色固体の２−（５，５−ジメチル−１，３，２−ジオキサボリナン−２−イル）アセトフェノンの生成を得た（１６９ｍｇ，収率７３％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．１２（６Ｈ，ｓ），２．６１（３Ｈ，ｓ），３．８０（３Ｈ，ｓ），７．３８−７．４２（１Ｈ，ｍ），７．５２−７．５４（２Ｈ，ｍ），７．８１（１Ｈ，ｄ，Ｊ＝７．７Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, ethyl 2-bromobenzoate (1.00 mmol, 229 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,2-dimethyl-1,3-propanediol (2.20 mmol, 229 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, hexane extraction was performed. The solution was filtered, the filtrate was concentrated, and the resulting residue was distilled to produce 2- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) acetophenone as a white solid. Obtained (169 mg, 73% yield).
¹ H-NMR (deuterated chloroform, ppm): δ 1.12 (6H, s), 2.61 (3H, s), 3.80 (3H, s), 7.38-7.42 (1H, m) 7.52-7.54 (2H, m), 7.81 (1H, d, J = 7.7 Hz).

  Example-119

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に２−ブロモアセトフェノン（１．００ｍｍｏｌ，１９９ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，２−ジメチル−１，３−プロパンジオール（２．２０ｍｍｏｌ，２２９ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、ヘキサンで抽出した。その溶液を濃縮することにより、無色液体の２−（５，５−ジメチル−１，３，２−ジオキサボリナン−２−イル）安息香酸エチルを得た（２４６ｍｇ，収率９４％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．１１（６Ｈ，ｓ）， １．３９（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ）， ３．７９（４Ｈ，ｓ）， ４．３８（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），７．３５−７．３９（１Ｈ，ｍ）， ７．４９−７．５０（２Ｈ，ｍ）， ７．９３（１Ｈ，ｄ，Ｊ＝７．７Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. 2-Bromoacetophenone (1.00 mmol, 199 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,2-dimethyl-1,3-propanediol (2.20 mmol, 229 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, the mixture was extracted with hexane. The solution was concentrated to obtain colorless liquid ethyl 2- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) benzoate (246 mg, yield 94%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.11 (6H, s), 1.39 (3H, t, J = 7.1 Hz), 3.79 (4H, s), 4.38 (2H, q, J = 7.1 Hz), 7.35-7.39 (1H, m), 7.49-7.50 (2H, m), 7.93 (1H, d, J = 7.7 Hz).

  Example-120

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に２−ブロモクロロベンゼン（１．００ｍｍｏｌ，１９１ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，２−ジメチル−１，３−プロパンジオール（２．２０ｍｍｏｌ，２２９ｍｇ）を加えて、室温でさらに３０分攪拌した。反応終了後、溶液をろ過し、酢酸エチルで洗った。濃縮後、反応混合物に水を加え、ジエチルエーテルで抽出した。その有機層をろ過し、ろ液を濃縮し、得られた残渣を蒸留することにより、無色液体の白色固体の２−（２−クロロフェニル）−５，５−ジメチル−１，３，２−ジオキサボリナンを得た（１３７ｍｇ，収率６１％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．０５（６Ｈ，ｓ），３．７９（４Ｈ，ｓ），７．２１（１Ｈ，ｔ，Ｊ＝７．３Ｈｚ），７．３０−７．３４（２Ｈ，ｍ）， ７．６３（１Ｈ， ｄ，Ｊ＝７．３Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 2-Bromochlorobenzene (1.00 mmol, 191 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,2-dimethyl-1,3-propanediol (2.20 mmol, 229 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of the reaction, the solution was filtered and washed with ethyl acetate. After concentration, water was added to the reaction mixture, and the mixture was extracted with diethyl ether. The organic layer was filtered, the filtrate was concentrated, and the resulting residue was distilled to give 2- (2-chlorophenyl) -5,5-dimethyl-1,3,2-dioxaborinane as a colorless liquid as a white solid. (137 mg, 61% yield) was obtained.
¹ H-NMR (deuterated chloroform, ppm): δ 1.05 (6H, s), 3.79 (4H, s), 7.21 (1H, t, J = 7.3 Hz), 7.30-7. 34 (2H, m), 7.63 (1H, d, J = 7.3 Hz).

Example-121
The same operation was carried out except that trifluoroethanol (6.0 mL) was used instead of dimethyl sulfoxide in Example-13, and 4- (4,4,5,5-tetramethyl-1,3,2) was used. The formation of -dioxaborolan-2-yl) methyl benzoate was confirmed by ¹ H NMR (NMR yield 18%).

Example-122
The same procedure was followed except that 1,3-dimethyl-2-imidazolidone (6.0 mL) was used instead of dimethyl sulfoxide in Example-13, and 4- (4,4,5,5-tetramethyl was used. The formation of methyl -1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example-123
The same procedure was followed except that N-methyl-2-pyrrolidone (6.0 mL) was used instead of dimethyl sulfoxide in Example-13, and 4- (4,4,5,5-tetramethyl-1 was used. , 3,2-Dioxaborolan-2-yl) methyl benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example-124
The same operation was carried out except that cyclopentyl methyl ether (6.0 mL) was used instead of dimethyl sulfoxide in Example-13, and 4- (4,4,5,5-tetramethyl-1,3,2) was used. The formation of -dioxaborolan-2-yl) methyl benzoate was confirmed by ¹ H NMR (NMR yield 42%).

Example-125
The same procedure was followed except that acetonitrile (6.0 mL) was used instead of dimethyl sulfoxide in Example-13, and 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used. The production of methyl-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 78%).

Example-126
The same operation was performed except that propanol (6.0 mL) was used instead of ethanol (6.0 mL) in Example 1, and 4- (4,4,5,5-tetramethyl-1,3 was used. , 2-Dioxaborolan-2-yl) methyl benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example-127
The same operation was performed except that 2-propanol (6.0 mL) was used instead of ethanol (6.0 mL) in Example 1, and 4- (4,4,5,5-tetramethyl-1 was used. , 3,2-Dioxaborolan-2-yl) methyl benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example-128
The same operation was performed except that ethylene glycol (6.0 mL) was used instead of ethanol (6.0 mL) in Example 1, and 4- (4,4,5,5-tetramethyl-1, The formation of methyl 3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 50%).

Example-129
The same operation was performed except that cyclohexanol (6.0 mL) was used instead of ethanol (6.0 mL) in Example 1, and 4- (4,4,5,5-tetramethyl-1, The formation of methyl 3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 86%).

Example-130
The same operation was performed except that hexanol (6.0 mL) was used instead of ethanol (6.0 mL) in Example 1, and 4- (4,4,5,5-tetramethyl-1,3 was used. , 2-Dioxaborolan-2-yl) methyl benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example-131
All the same operations were performed except that 2,3-dimethyl-2,3-butanediol of Example-13 was changed to (1.10 mmol, 130 mg), and 4- (4,4,5,5-tetramethyl- The formation of methyl 1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 91%).

  Example-132

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−クロロ安息香酸メチル（１．００ｍｍｏｌ，１７１ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルの生成を確認した（ＮＭＲ収率２７％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３６（１２Ｈ，ｓ），３．９２（３Ｈ，ｓ），７．８７（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ），８．０２（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ）．
ＭＳ（ｍ／ｚ）：２６２［Ｍ］^＋。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, methyl 4-chlorobenzoate (1.00 mmol, 171 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. The production of methyl 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 27%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.36 (12H, s), 3.92 (3H, s), 7.87 (2H, d, J = 8.4 Hz), 8.02 (2H, d, J = 8.4 Hz).
MS (m / z): 262 [M] ^<+> .

Example-133
The same procedure as in Example 132 was performed except that dimethyl sulfoxide (6.0 mL) was used instead of ethanol (6.0 mL), and potassium acetate (7.20 mmol, 706 mg) was used. The formation of methyl 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 29%).

  Example-134

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ安息香酸エチル（１．００ｍｍｏｌ，２２９ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、１，２−エタンジオール（２．２０ｍｍｏｌ，１３７ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより４−（１，３，２−ジオキサボロラン−２−イル）安息香酸エチルの生成を確認した（ＮＭＲ収率９９％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．４０（３Ｈ，ｔ，Ｊ＝７．０Ｈｚ），４．３８（２Ｈ，ｑ，Ｊ＝７．０Ｈｚ），４．４１（４Ｈ，ｓ），７．８８（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ），８．０４（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, ethyl 4-bromobenzoate (1.00 mmol, 229 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 1,2-ethanediol (2.20 mmol, 137 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. ¹ H NMR confirmed the formation of ethyl 4- (1,3,2-dioxaborolan-2-yl) benzoate (NMR yield 99%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.40 (3H, t, J = 7.0 Hz), 4.38 (2H, q, J = 7.0 Hz), 4.41 (4H, s), 7.88 (2H, d, J = 8.4 Hz), 8.04 (2H, d, J = 8.4 Hz).

Example-135
The same procedure as in Example 134 was performed except that dimethyl sulfoxide (6.0 mL) was used instead of ethanol (6.0 mL) and potassium acetate (7.20 mmol, 706 mg) was used, and 4- (1, The formation of ethyl 3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

  Example-136

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（３．００ｍｍｏｌ，２９４ｍｇ）を加えてアルゴン置換した。さらにエタノール（６．０ｍＬ）を加えた。この反応溶液に４−ブロモ安息香酸エチル（１．００ｍｍｏｌ，２２９ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、１，３−プロパンジオール（２．２０ｍｍｏｌ，１６３ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより４−（１，３，２−ジオキサボリナン−２−イル）安息香酸エチルの生成を確認した（ＮＭＲ収率９９％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．４０（３Ｈ，ｔ，Ｊ＝７．０Ｈｚ），２．０８（２Ｈ，ｑｕｉｎｔ，Ｊ＝５．５Ｈｚ），４．１８（４Ｈ，ｔ，Ｊ＝５．５Ｈｚ），４．３８（２Ｈ，ｑ，Ｊ＝７．０Ｈｚ），７．８３（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ），８．００（２Ｈ，ｄ，Ｊ＝８．４Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (3.00 mmol, 294 mg) were added, and the atmosphere was replaced with argon. Further ethanol (6.0 mL) was added. To this reaction solution, ethyl 4-bromobenzoate (1.00 mmol, 229 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 1,3-propanediol (2.20 mmol, 163 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. The production of ethyl 4- (1,3,2-dioxaborinan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.40 (3H, t, J = 7.0 Hz), 2.08 (2H, quint, J = 5.5 Hz), 4.18 (4H, t, J = 5.5 Hz), 4.38 (2H, q, J = 7.0 Hz), 7.83 (2H, d, J = 8.4 Hz), 8.00 (2H, d, J = 8.4 Hz) .

Example-137
The same operation was carried out except that dimethyl sulfoxide (6.0 mL) was used instead of ethanol (6.0 mL) in Example-136, and potassium acetate (7.20 mmol, 706 mg) was used, and 4- (1, Formation of ethyl 3,2-dioxaborinan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

  Example-138

反応容器に、２，２’−ビ（１，３，２−ベンゾジオキサボロール）（１．１０ｍｍｏｌ，２６２ｍｇ）、ジクロロ［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（０．０３０ｍｍｏｌ，２５ｍｇ）、酢酸カリウム（７．２０ｍｍｏｌ，７０６ｍｇ）を加えてアルゴン置換した。さらにジメチルスルホキシド（６．０ｍＬ）を加えた。この反応溶液に４−ブロモビフェニル（１．００ｍｍｏｌ，２３３ｍｇ）を加えて８０℃で２時間攪拌した。室温まで冷却後、２，３−ジメチル−２，３−ブタンジオール（２．２０ｍｍｏｌ，２６０ｍｇ）を加えて、室温でさらに３０分攪拌した。^１Ｈ ＮＭＲにより４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ビフェニルの生成を確認した（ＮＭＲ収率９９％）。
^１Ｈ−ＮＭＲ（重クロロホルム，ｐｐｍ）：δ１．３６（１２Ｈ，ｓ），７．４５（２Ｈ，ｄ，Ｊ＝７．９Ｈｚ），７．６１（５Ｈ， ｍ），７．８８（２Ｈ，ｄ，Ｊ＝７．９Ｈｚ）。

In a reaction vessel, 2,2′-bi (1,3,2-benzodioxaborole) (1.10 mmol, 262 mg), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (0. 030 mmol, 25 mg) and potassium acetate (7.20 mmol, 706 mg) were added, and the atmosphere was replaced with argon. Further dimethyl sulfoxide (6.0 mL) was added. 4-Bromobiphenyl (1.00 mmol, 233 mg) was added to the reaction solution, and the mixture was stirred at 80 ° C. for 2 hours. After cooling to room temperature, 2,3-dimethyl-2,3-butanediol (2.20 mmol, 260 mg) was added, and the mixture was further stirred at room temperature for 30 minutes. The formation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) biphenyl was confirmed by ¹ H NMR (NMR yield 99%).
¹ H-NMR (deuterated chloroform, ppm): δ 1.36 (12H, s), 7.45 (2H, d, J = 7.9 Hz), 7.61 (5H, m), 7.88 (2H, d, J = 7.9 Hz).

Example-139
The same operation was carried out except that ethanol potassium (6.0 mL) was used instead of dimethyl sulfoxide in an amount of 3.00 mmol (294 mg) of potassium acetate in Example 138, and 4- (4, 4, 5, 5- The formation of tetramethyl-1,3,2-dioxaborolan-2-yl) biphenyl was confirmed by ¹ H NMR (NMR yield 90%).

Example 140
All the same operations were carried out except that 0.020 mmol of dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium in Example-13 was used, and 4- (4,4,5,5-tetramethyl- The formation of methyl 1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Example 141
All the same operations were performed except that 0.005 mmol of dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium in Example-13 was used, and 4- (4,4,5,5-tetramethyl- The formation of methyl 1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 80%).

Example 142
All the same operations were performed except that 0.005 mmol of dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium in Example-1 was used, and 4- (4,4,5,5-tetramethyl- The formation of methyl 1,3,2-dioxaborolan-2-yl) benzoate was confirmed by ¹ H NMR (NMR yield 99%).

Claims (3)

In the presence of a palladium catalyst and acetate, the general formula (1)

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) and a general formula (2)

Wherein R ² is a hydrogen atom; a C 1-6 alkyl group optionally substituted with a fluorine atom, a hydroxyl group or an amino group; a C 1-4 alkoxy optionally substituted with a fluorine atom A phenyloxy group optionally substituted by an alkyl group having 1 to 4 carbon atoms; (an alkyl having 1 to 4 carbon atoms) carbonyl group; (an alkoxy having 1 to 4 carbon atoms) carbonyl group; a carboxyl group; a formyl group A hydroxyl group, a halogen atom, a cyano group, a phenyl group optionally substituted by an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms or a (carbonyl group having 1 to 4 alkyl) carbonyl group. And an amino group that may be substituted; a carbamoyl group; (an alkyl having 1 to 4 carbon atoms that may be substituted with a fluorine atom) thio group; a sulfamoyl group; a fluorosulfonyl group; (Phenyl optionally substituted with a fluorine atom) oxysulfonyl group; or a phenyl group, adjacent hydroxyl groups may form together an alkylenedioxy group having 1 to 3 carbon atoms. Represents 1 to 4. X represents a chlorine atom, a bromine atom, an iodine atom, or a trifluoromethylsulfonyloxy group), and then reacted with a benzene derivative represented by the general formula (3)

(Wherein R ³ and R ⁴ are the same or different and each represents a hydrogen atom or a methyl group. A represents a methylene group; a dimethylmethylene group; an ethylene group; or a single bond). General formula (4)

(Wherein R ² , R ³ , R ⁴ , n and A have the same contents as above), a method for producing aryl (diolate) boranes. The production method according to claim 1, wherein R ¹ is a hydrogen atom or a tert-butyl group. The production method according to claim 1 or 2, wherein the acetate is potassium acetate or sodium acetate.