JP5072026B2

JP5072026B2 - Method for producing homoallyl alcohol or homoallyl hydrazide

Info

Publication number: JP5072026B2
Application number: JP2008018887A
Authority: JP
Inventors: 修小林; シュナイダーウーベ; 雅晴上野
Original assignee: Japan Science and Technology Agency; National Institute of Japan Science and Technology Agency
Current assignee: Japan Science and Technology Agency; National Institute of Japan Science and Technology Agency
Priority date: 2007-03-09
Filing date: 2008-01-30
Publication date: 2012-11-14
Anticipated expiration: 2028-01-30
Also published as: JP2008255093A

Description

この発明は、アリル化剤によってケトン又はN-アシルヒドラゾンをアリル化するホモアリルアルコール又はホモアリルヒドラジドの製造方法に関する。 The present invention relates to a process for producing homoallyl alcohol or homoallyl hydrazide, wherein a ketone or N-acylhydrazone is allylated with an allylating agent.

ケトンのアリル化による生成物（例えば、三級ホモアリルアルコール）は有用な中間体であり、その効率的な製造方法の確立が要望されている。
一方、従来から、有機合成反応において０価のインジウムが広く用いられている。これは、０価のインジウムは容易に入手可能であり、無毒で安価、さらに使用前の活性化が通常は必要なく、水や水溶液の存在下でも活性を失わない等の利点によるものである。
インジウムを用いた反応としては、ハロゲン化アリルのBarbier型反応でアリルインジウム種が生成し、これが求電子剤と反応することが報告されている（非特許文献１参照）。又、近年、０価のインジウムがアリルパラジウム前駆体を対応するアリルインジウム試薬へ変換し、又は二級アルキルハライドを対応するアルキルラジカルへと変換する性質を有することが明らかにされている（非特許文献２参照）。 Products obtained by allylation of ketones (eg, tertiary homoallylic alcohol) are useful intermediates, and establishment of an efficient production method is desired.
On the other hand, zero-valent indium has been widely used in organic synthesis reactions. This is because zero-valent indium is easily available, is non-toxic and inexpensive, and does not normally require activation before use, and does not lose its activity even in the presence of water or an aqueous solution.
As a reaction using indium, it has been reported that an allylindium species is generated by a Barbier-type reaction of an allyl halide and reacts with an electrophile (see Non-Patent Document 1). In recent years, it has been clarified that zero-valent indium has a property of converting an allyl palladium precursor into a corresponding allyl indium reagent or converting a secondary alkyl halide into a corresponding alkyl radical (non-patent document). Reference 2).

又、イミン類のアリル化は重要な炭素-炭素結合生成物であり（非特許文献３）、生成物のホモアリルアミン類は整理活性物質等の有用な中間体となる（非特許文献４）。イミンのアリル化は、通常はハロゲン化アリルをBarbier型反応条件で調製したアリルインジウム試薬を用いるが（非特許文献５）、最近ではアリルパラジウム（非特許文献６）やアリル水銀（非特許文献７）から金属交換反応でアリルインジウムを調製する方法も報告されている。
しかしながら、他のアリル化反応方法では毒性の高いアリルスズ（非特許文献８）や腐食性のあるアリルケイ素試薬（非特許文献９）、又は活性化されたイミン誘導体（非特許文献１０）を用いる必要がある。一方、アシルヒドラゾン類は対応するカルボニル化合物から調製され、イミンに比べて非常に安定性が高い（非特許文献１１）。しかしながらアシルヒドラゾンを用いる触媒的アリル化反応は、ごく限られた基質でしか報告されていない（非特許文献１２）。 In addition, allylation of imines is an important carbon-carbon bond product (Non-patent Document 3), and the product homoallylamines are useful intermediates such as organizing active substances (Non-patent Document 4). For the allylation of imine, an allyl indium reagent prepared from an allyl halide under Barbier-type reaction conditions is usually used (Non-Patent Document 5). Recently, allyl palladium (Non-Patent Document 6) and allyl mercury (Non-Patent Document 7) are used. ) To prepare allylindium by a metal exchange reaction.
However, other allylation methods require the use of highly toxic allyltin (Non-patent Document 8), corrosive allylsilicon reagent (Non-patent Document 9), or an activated imine derivative (Non-patent Document 10). There is. On the other hand, acyl hydrazones are prepared from the corresponding carbonyl compounds and are very stable compared to imines (Non-patent Document 11). However, catalytic allylation reaction using acyl hydrazone has been reported only with a very limited substrate (Non-patent Document 12).

L. A. Paquette, T. M. Mitzel, J. Am. Chem. Soc. 1996, 118, 1931-1937L. A. Paquette, T. M. Mitzel, J. Am. Chem. Soc. 1996, 118, 1931-1937 H. Miyabe, T. Naito, Org. Biomol. Chem. 2004, 2, 1267-1270H. Miyabe, T. Naito, Org. Biomol. Chem. 2004, 2, 1267-1270 Kobayashi, S.; Ishitani, H. Chem. Rev. 1999, 99, 1069Kobayashi, S .; Ishitani, H. Chem. Rev. 1999, 99, 1069 Ding, H.; Friestad, G. K. Synthesis 2005, 2815Ding, H .; Friestad, G. K. Synthesis 2005, 2815 Loh, T.-P.; Ho, D. S.-C.; Xu, K.-C.; Sim, K.-Y. Tetrahedron Lett. 1997, 38, 865Loh, T.-P .; Ho, D. S.-C .; Xu, K.-C .; Sim, K.-Y. Tetrahedron Lett. 1997, 38, 865 Cooper, I. R.; Grigg, R.; MacLachlan, W. S.; Sridharan, V.; Thornton-Pett, M. Tetrahedron Lett. 2003, 44, 403Cooper, I. R .; Grigg, R .; MacLachlan, W. S .; Sridharan, V .; Thornton-Pett, M. Tetrahedron Lett. 2003, 44, 403 Chan, T. H.; Yang, Y. J. Am. Chem. Soc. 1999, 121, 3228Chan, T. H .; Yang, Y. J. Am. Chem. Soc. 1999, 121, 3228 Nakamura, H.; Nakamura, K.; Yamamoto, Y. J. Am. Chem. Soc. 1998, 120, 4242Nakamura, H .; Nakamura, K .; Yamamoto, Y. J. Am. Chem. Soc. 1998, 120, 4242 Nakamura, K.; Nakamura, H.; Yamamoto, Y. J. Org. Chem. 1999, 64, 2614Nakamura, K .; Nakamura, H .; Yamamoto, Y. J. Org. Chem. 1999, 64, 2614 Ferraris, D.; Dudding, T.; Young, B.; Drury, W. J. III; Lectka, T. J. Org. Chem. 1999, 64, 2168Ferraris, D .; Dudding, T .; Young, B .; Drury, W. J. III; Lectka, T. J. Org. Chem. 1999, 64, 2168 Oyamada, H.; Kobayashi, S. Synlett 1998, 249Oyamada, H .; Kobayashi, S. Synlett 1998, 249 Cook, G. R.; Maity, B. C.; Kargbo, R. Org. Lett. 2004, 6, 1741Cook, G. R .; Maity, B. C .; Kargbo, R. Org. Lett. 2004, 6, 1741

しかしながら、上記した従来技術の場合、化学量論量（基質と同一の量）のインジウムが必要であるという問題があった。
従って、本発明は、触媒量のインジウムを用いてケトン又はN-アシルヒドラゾンをアリル化するホモアリルアルコール又はホモアリルヒドラジドの製造方法の提供を目的とする。 However, the above-described conventional technique has a problem that a stoichiometric amount (the same amount as the substrate) of indium is necessary.
Accordingly, an object of the present invention is to provide a method for producing homoallyl alcohol or homoallyl hydrazide, in which a ketone or N-acylhydrazone is allylated using a catalytic amount of indium.

このような課題を解決するために、本発明者らは鋭意研究した結果、ホウ素を含むアリル化剤を用いることにより、触媒量のインジウムでアリル化反応が進行することを見出し、本発明を完成するに至った。 In order to solve such problems, the present inventors have intensively researched and found that by using an allylating agent containing boron, the allylation reaction proceeds with a catalytic amount of indium, and the present invention has been completed. It came to do.

即ち、本発明のホモアリルアルコール又はホモアリルヒドラジドの製造方法は、式I

で表されるピナコリルアリルボレートからなるホウ素を含むアリル化剤によってケトン又はN-アシルヒドラゾンをアリル化し、前記ケトン又はN-アシルヒドラゾンに対し１〜５０mol%の１価又は０価のインジウムを触媒として用いるホモアリルアルコール又はホモアリルヒドラジドの製造方法であって、前記ケトンは、Ｒ _１ -Ｃ＝Ｏ-Ｒ _２（Ｒ _１，Ｒ _２は、芳香族基、複素環基、脂肪族基）で表され、前記N-アシルヒドラゾンは、式XXIX

（式中、Ｒ ^４は芳香族基、脂肪族基又は複素環基；Ｒ ^５は水素原子又は脂肪族基；Ｒ ^６は芳香族基）で表される。 That is, the method for producing homoallyl alcohol or homoallyl hydrazide of the present invention has the formula I

A ketone or N-acylhydrazone is allylated with a boron-containing allylating agent consisting of pinacolylallylborate represented by the formula: 1-50 mol% of monovalent or zero-valent indium with respect to the ketone or N-acylhydrazone. A method for producing homoallyl alcohol or homoallyl hydrazide used as a catalyst, wherein the ketone is R ₁ —C═O—R ₂ (R ₁ and R ₂ are aromatic groups, heterocyclic groups, aliphatic groups) And the N-acylhydrazone is represented by the formula XXIX

(Wherein R ⁴ is an aromatic group, aliphatic group or heterocyclic group; R ⁵ is a hydrogen atom or aliphatic group; R ⁶ is an aromatic group) .

本発明によれば、触媒量のインジウムを用いてケトン又はN-アシルヒドラゾンをアリルボロネートによりアリル化することができる。 According to the present invention, a ketone or N-acyl hydrazone can be allylated with an allyl boronate using a catalytic amount of indium.

本発明は、触媒量のインジウムの存在下、ホウ素を含むアリル化剤によってケトン又はN-アシルヒドラゾンをアリル化するものである。
ホウ素を含むアリル化剤としては、以下の式II

に示すアリルボロネート（Ｒは水素原子または脂肪族炭化水素基をあらわす）又はアリルボレートが挙げられる。
特に、アリル化剤として、式I

で表されるピコナールアリルボレートを用いることが好ましい。 In the present invention, a ketone or N-acyl hydrazone is allylated with an allylating agent containing boron in the presence of a catalytic amount of indium.
As an allylating agent containing boron, the following formula II

And allyl boronate (R represents a hydrogen atom or an aliphatic hydrocarbon group) or allyl borate.
In particular, as an allylating agent, the formula I

It is preferable to use piconal allyl borate represented by:

一価のインジウムの場合、ホウ素原子と置換する（トランスメタル化）ことで高活性なアリルインジウムが生成するか、又はインジウムがホウ素原子に配位することでアリルボロネートの活性が向上すると考えられる。０価のインジウムの場合は、前述のトランスメタル化、又は、インジウムから一電子がホウ素に移動することによりラジカル機構で反応が進行していると考えられる。 In the case of monovalent indium, substitution of a boron atom (transmetallation) generates highly active allylindium, or the coordination of indium to the boron atom improves the activity of allylboronate. . In the case of zero-valent indium, it is considered that the reaction proceeds by the radical mechanism by the above-mentioned transmetalation or by transfer of one electron from indium to boron.

ケトンとしては、特に制限されず、例えば、環式ケトン、非環式ケトン、芳香族ケトン、複素環ケトン、脂肪族ケトン等を用いることができる。つまり本発明は、広い基質一般性を有する。又、ケトンとしては、アミノ基、水酸基、メトキシ基、クロロ基、ブロモ基、ニトロ基、アミド基などの種々の官能基を構造に含むものを用いることができる。
又、式XXIX

（式中、Ｒ^４は芳香族基、脂肪族基又は複素環基；Ｒ^５は水素原子又は脂肪族基；Ｒ^６は芳香族基）で表されるN-アシルヒドラゾンを用いることもできる。 The ketone is not particularly limited, and for example, a cyclic ketone, an acyclic ketone, an aromatic ketone, a heterocyclic ketone, an aliphatic ketone, or the like can be used. That is, the present invention has a broad substrate generality. In addition, as the ketone, those having various functional groups such as amino group, hydroxyl group, methoxy group, chloro group, bromo group, nitro group, amide group in the structure can be used.
Also, the formula XXIX

N-acylhydrazone represented by the formula (wherein R ⁴ is an aromatic group, aliphatic group or heterocyclic group; R ⁵ is a hydrogen atom or aliphatic group; R ⁶ is an aromatic group) can also be used.

ケトン及びN-アシルヒドラゾンのアリル化の触媒として、前記ケトン又はN-アシルヒドラゾンに対し１〜５０mol%の１価又は０価のインジウムを用いる。前記ケトンに対するインジウムの量は、好ましくは１〜２０mol%、より好ましくは５〜２０mol%である。
１価のインジウムとしては、ヨウ化インジウム、臭化インジウム、塩化インジウム等のハロゲン化インジウム、またはインジウムトリフラートを好適に用いることができる。本発明で用いるインジウムは、水又は有機溶媒中に溶解又は分散させて用いることができ、有機溶媒としては、テトラヒドロフラン、塩化メチレン、エタノール、ジメチルホルムアミド、アセトニトリルを例示することができる。特に、水を溶媒とする場合は、環境負荷が少なくなる。
但し、N-アシルヒドラゾンのアリル化においては、溶媒としてトルエンにメタノールを加えた系が適しており、水を溶媒とすると収率が低下する傾向にある。 As a catalyst for allylation of a ketone and N-acyl hydrazone, 1 to 50 mol% of monovalent or zero-valent indium is used with respect to the ketone or N-acyl hydrazone. The amount of indium with respect to the ketone is preferably 1 to 20 mol%, more preferably 5 to 20 mol%.
As monovalent indium, indium halides such as indium iodide, indium bromide, and indium chloride, or indium triflate can be suitably used. Indium used in the present invention can be used by dissolving or dispersing in water or an organic solvent, and examples of the organic solvent include tetrahydrofuran, methylene chloride, ethanol, dimethylformamide, and acetonitrile. In particular, when water is used as a solvent, the environmental burden is reduced.
However, in the allylation of N-acylhydrazone, a system in which methanol is added to toluene as a solvent is suitable, and when water is used as a solvent, the yield tends to decrease.

本発明において、反応系の溶媒中の各成分の濃度はそれぞれ0.01〜5mol/lであることが好ましい。
この反応の温度は、好ましくは-78〜60℃である。
この反応時間は、数分〜数１０時間程度である。
この反応系には上記成分のほか、適宜、触媒や界面活性剤等の公知の添加剤を添加してもよい。 In the present invention, the concentration of each component in the solvent of the reaction system is preferably 0.01 to 5 mol / l.
The temperature of this reaction is preferably -78 to 60 ° C.
This reaction time is about several minutes to several tens of hours.
In addition to the above components, known additives such as catalysts and surfactants may be added to this reaction system as appropriate.

本発明の製造方法によって得られる生成物としては、２−フェニルー４−ペンテンー２−オール等、様々な置換基を有する三級ホモアリルアルコール又はホモアリルヒドラジドを例示することができる。
生成物は、抽出、カラムクロマトグラフィー、蒸留、再結晶等の一般的精製法を利用して回収できる。 Examples of the product obtained by the production method of the present invention include tertiary homoallyl alcohol or homoallyl hydrazide having various substituents such as 2-phenyl-4-penten-2-ol.
The product can be recovered using common purification methods such as extraction, column chromatography, distillation, recrystallization and the like.

R₁R₂=Oで表されるケトンに対し、式Iで表されるピコナールアリルボレートをアリル化剤として用いた場合の反応式を式III

に示す。
ここで、R₁，R₂としては、芳香族基、複素環基、脂肪族基等が挙げられる。 For the ketone represented by R ₁ R ₂ ═O, the reaction formula when piconal allyl borate represented by formula I is used as the allylating agent is represented by formula III

Shown in
Here, examples of R ₁ and R ₂ include aromatic groups, heterocyclic groups, and aliphatic groups.

以下、実施例にて本発明を例証するが本発明を限定することを意図するものではない。 The following examples illustrate the invention but are not intended to limit the invention.

なお、以下の各実施例において、特に記載しない限り、全ての溶媒とケトン（市販のもの）は使用前にアルゴン下で蒸留又は再結晶した。市販品であるピナコールアリルボロネート2は既知法（Y.-C. Teo, J.-D. Goh, T.-P. Loh, Org. Lett. 2005, 7, 2743-2745）の改良法で調製した。
インジウム触媒として、ヨウ化インジウム(I) (10mesh-beads or powdered form; 99.999%), 塩化インジウム(I) (powder; 99.999%), 臭化インジウム(I) (10 mesh-beads or powdered form; 99.999%), 0価インジウム (100 mesh-powder; 99.99%), ヨウ化インジウム(III)(powder; 99.998%), インジウム(III)トリフラート (powder, 99+%))、InCl3(anhydrous powder, 99.999%),InBr3(anhydrous powder, 99.999%), In(OH)3(nanopowder, 99.99%)は全てAldrich社の市販品であり, さらなる精製を行わずに用いた。全ての反応操作は乾燥したガラス器具を用い、アルゴン下で行った。 In the following Examples, all solvents and ketones (commercially available) were distilled or recrystallized under argon before use unless otherwise specified. Commercially available pinacol allylboronate 2 is an improved method of the known method (Y.-C. Teo, J.-D. Goh, T.-P. Loh, Org. Lett. 2005, 7, 2743-2745). Prepared.
As indium catalyst, indium iodide (I) (10mesh-beads or powdered form; 99.999%), indium chloride (I) (powder; 99.999%), indium bromide (I) (10 mesh-beads or powdered form; 99.999 %), 0-valent indium (100 mesh-powder; 99.99%), indium (III) iodide (powder; 99.998%), indium (III) triflate (powder, 99 +%)), InCl3 (anhydrous powder, 99.999% ), InBr3 (anhydrous powder, 99.999%) and In (OH) 3 (nanopowder, 99.99%) were all commercially available from Aldrich and were used without further purification. All reaction operations were performed under argon using dry glassware.

又、生成物の同定は、以下のNMR,IR,マススペクトル、及びクロマトグラフィーを用いた。NMR スペクトルは日本電子製のJEOL JNM-ECX400 を用い CDCl₃ もしくはDMSO-d₆.中で測定し、テトラメチルシラン(TMS; δ = 0.00 ppm) 及び非重水素化DMSO シグナル (δ = 2.49 ppm) を ¹H NMRの内部標準とした。また、次の非重水素化溶媒シグナル (CDCl₃: δ = 77.00 ppm; DMSO-d₆: δ = 39.50 ppm) を¹³C NMRの内部標準として用いた。IR スペクトルはJASCO FT/IR-610 を用いて測定した。ESI 高分解能マススペクトル(ESI-HRMS) はブルカダルトニクスBioTOF IIを用いて測定した。カラムクロマトグラフィーはSilica gel 60 (Merck) を用い、分取用薄層クロマトグラフィーはWakogel B-5Fを用いて行った。 The product was identified using the following NMR, IR, mass spectrum, and chromatography. NMR spectra were measured in CDCl ₃ or DMSO-d ₆ using JEOL JNM-ECX400 manufactured by JEOL. Tetramethylsilane (TMS; δ = 0.00 ppm) and non-deuterated DMSO signal (δ = 2.49 ppm) Was used as an internal standard for ¹ H NMR. The following non-deuterated solvent signal (CDCl ₃ : δ = 77.00 ppm; DMSO-d ₆ : δ = 39.50 ppm) was used as an internal standard for ¹³ C NMR. The IR spectrum was measured using JASCO FT / IR-610. ESI high-resolution mass spectra (ESI-HRMS) were measured using a Brucadartonics BioTOF II. Column chromatography was performed using Silica gel 60 (Merck), and preparative thin layer chromatography was performed using Wakogel B-5F.

<種々のインジウム触媒による、水中でのケトンのアリル化>
セプタム栓をし、乾燥した10mLの攪拌子入りシュレンク型フラスコに、アルゴン雰囲気下、純水（2.5ml,0.2mol/L）及び、上記した各種インジウム触媒20mol%を加えた後、ケトン1(0.5mmol) およびピナコールアリルボロネート 2（ 0.75mmol; 1.5equiv）を順次加えた。アルゴン雰囲気下、４０℃で２４時間激しく攪拌し、塩化メチレンで希釈した後に飽和炭酸水素ナトリウ水溶液を加えた。相分離後、水相から塩化メチレンで三回の抽出を行い、有機相を合わせて硫酸ナトリウムで乾燥し、濾過の後に減圧濃縮した。残さをシリカゲルクロマトグラフィー（溶媒:n-ヘキサン/酢酸エチル=99:1〜1:1）にて精製し、対応する三級ホモアリルアルコール3を得た。
反応式を式IV

に示す。 <Allylation of ketones in water with various indium catalysts>
After adding a septum stopper and adding 10 mL of pure water (2.5 ml, 0.2 mol / L) and the above-mentioned various indium catalysts to an argon atmosphere in a Schlenk flask containing a 10 mL stir bar and drying, ketone 1 (0.5 mmol) and pinacol allylboronate 2 (0.75 mmol; 1.5 equiv) were added sequentially. In an argon atmosphere, the mixture was vigorously stirred at 40 ° C. for 24 hours, diluted with methylene chloride, and then a saturated aqueous sodium hydrogen carbonate solution was added. After phase separation, the aqueous phase was extracted three times with methylene chloride, the organic phases were combined, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography (solvent: n-hexane / ethyl acetate = 99: 1 to 1: 1) to obtain the corresponding tertiary homoallylic alcohol 3.
Formula IV

Shown in

実施例１で得られた結果を表１に示す。 The results obtained in Example 1 are shown in Table 1.

表１より、１価のインジウム（特に、InBr,InI）を用いた場合に収率が最も高くなった。 From Table 1, the yield was highest when monovalent indium (particularly InBr, InI) was used.

<種々のインジウム触媒による、ＴＨＦ中でのケトンのアリル化>
溶媒として純水の代わりにテトラヒドロフラン（THF;2.5ml,0.2mol/L）を用い、インジウム触媒の添加量を表２に示すように変化させたこと以外は、実施例１とまったく同様にして三級ホモアリルアルコール3を得た。
実施例２で得られた結果を表２に示す。 <Allylation of ketones in THF with various indium catalysts>
Three steps were performed in exactly the same manner as in Example 1 except that tetrahydrofuran (THF; 2.5 ml, 0.2 mol / L) was used as the solvent instead of pure water and the addition amount of the indium catalyst was changed as shown in Table 2. Grade homoallylic alcohol 3 was obtained.
The results obtained in Example 2 are shown in Table 2.

表２より、一価のインジウム触媒の量を1 mol%にまで減らしても反応が収率よく進行した。１価のインジウム触媒の中ではヨウ化インジウムが良好であった。また、０価のインジウム触媒や３価のインジウム触媒はそれぞれ単独では反応はほとんど進行しないが、０価と３価のインジウム触媒と共に用いると反応が進行した。これは系内で１価のインジウムが生成しているためと思われる。 From Table 2, the reaction proceeded with good yield even when the amount of monovalent indium catalyst was reduced to 1 mol%. Among the monovalent indium catalysts, indium iodide was good. In addition, although the zero-valent indium catalyst and the trivalent indium catalyst are each independent, the reaction hardly proceeds, but the reaction proceeds when used together with the zero-valent and trivalent indium catalysts. This is probably because monovalent indium is generated in the system.

<０価インジウムによる、種々の溶媒中でのケトンのアリル化>
溶媒として純水の代わりに表３に示すものを0.2mol/L用い、インジウム触媒として０価インジウムを用いたこと以外は、実施例１とまったく同様にして三級ホモアリルアルコール3を得た。
実施例３で得られた結果を表３に示す。 <Allylation of ketones in various solvents with zerovalent indium>
Tertiary homoallyl alcohol 3 was obtained in exactly the same manner as in Example 1 except that 0.2 mol / L of the solvent shown in Table 3 was used instead of pure water as a solvent and zerovalent indium was used as an indium catalyst.
The results obtained in Example 3 are shown in Table 3.

表３より、水中で高い収率を示すことが判明した。 From Table 3, it was found that a high yield was exhibited in water.

<種々のケトンに対する、ヨウ化インジウム触媒によるＴＨＦ中でのアリル化>
ケトン1の代わりに表４に示すケトンを用い、溶媒として純水の代わりにテトラヒドロフラン（THF;2.5ml,0.2mol/L）を用い、インジウム触媒としてヨウ化インジウム(I)（6.0mg;5mol%）用いたこと以外は、実施例１とまったく同様にして対応する三級ホモアリルアルコールを得た。
反応式を式III

に示す。
実施例４で得られた結果を表４に示す。 <Allylation of various ketones in THF with indium iodide catalyst>
The ketone shown in Table 4 was used instead of ketone 1, tetrahydrofuran (THF; 2.5 ml, 0.2 mol / L) was used instead of pure water as a solvent, and indium iodide (I) (6.0 mg; 5 mol%) as an indium catalyst. ) The corresponding tertiary homoallyl alcohol was obtained in the same manner as in Example 1 except that it was used.
Formula III

Shown in
The results obtained in Example 4 are shown in Table 4.

なお、表４におけるEntry1〜24は、それぞれ以下の生成物3a〜3xに対応するケトンと収率の組合せである。 In Table 4, Entry 1 to 24 are combinations of ketones and yields corresponding to the following products 3a to 3x, respectively.

生成物3a；2-Phenylpent-4-en-2-ol (3a; entry 1): ケトンとしてacetophenone (1a)を用いたときに淡黄色液体 (収率: 88%)として得られ、式V

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 1.55 (s, 3H), 2.08 (br s, 1H), 2.50 (dd, J = 8.4 Hz, J = 13.2 Hz, 1H), 2.69 (dd, J = 6.4 Hz, J = 13.2 Hz, 1H), 5.11-5.16 (m, 2H), 5.57-5.68 (m, 1H), 7.22-7.45 (m, 5H); ¹³C NMR (CDCl₃, 100 MHz): δ= 29.87, 48.43, 73.59, 119.44, 124.73, 126.59, 128.14, 133.65, 147.61; IR (neat): ν = 3433, 3075, 2978, 2930, 1639, 1494, 1446, 1374, 1069, 999, 915, 866, 767, 700, 658, 567 cm^-1; HRMS (ESI) calcd. for C₁₁H₁₃ ⁺ = [M-OH]⁺: m/z = 145.1012, found: m/z = 145.1008. Product 3a; 2-Phenylpent-4-en-2-ol (3a; entry 1): obtained as a pale yellow liquid (yield: 88%) when acetophenone (1a) is used as the ketone, formula V

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.55 (s, 3H), 2.08 (br s, 1H), 2.50 (dd, J = 8.4 Hz, J = 13.2 Hz, 1H), 2.69 (dd, J = 6.4 Hz, J = 13.2 Hz, 1H), 5.11-5.16 (m, 2H), 5.57-5.68 (m, 1H), 7.22-7.45 (m, 5H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 29.87, 48.43, 73.59, 119.44, 124.73, 126.59, 128.14, 133.65, 147.61; IR (neat): ν = 3433, 3075, 2978, 2930, 1639, 1494, 1446, 1374, 1069, 999, 915, 866 , 767, 700, 658, 567 cm ^-1 ; HRMS (ESI) calcd.for C ₁₁ H ₁₃ ⁺ = [M-OH] ⁺ : m / z = 145.1012, found: m / z = 145.1008.

生成物3b；5-(2-Hydroxypent-4-en-2-yl)benzene-1,3-diol(3b; entry 2): ケトンとして1-(3,5-dihydroxyphenyl)ethanone (1b)を用いたときに無色粘性液体 (収率: quant.)として得られ、式VI

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ=1.41 (s, 3H), 2.30 (br s, 1H), 2.36 (dd, J = 8.0 Hz, J = 13.6 Hz, 1H), 2.56 (dd, J = 6.4 Hz, J = 13.6 Hz, 1H), 5.00-5.09 (m, 2H), 5.50-5.63 (m, 1H), 6.20 (t, J = 2.4 Hz, 1H), 6.41 (d, J = 2.4 Hz, 2H), 6.80 (s, 2H); ¹³C NMR CDCl₃, 100 MHz): δ =29.59, 48.14, 73.77, 101.21, 104.31, 119.33, 133.70, 150.64, 157.26; IR (neat): ν = 3276, 2978, 2255, 1602, 1445, 1338, 1268, 1159, 1048, 1025, 1000, 918, 846, 736, 704 cm^-1; HRMS (ESI) calcd. for C₁₁H₁₃O₂ ⁺ = [M-OH]⁺: m/z = 177.0910, found: m/z = 177.0914. Product 3b; 5- (2-Hydroxypent-4-en-2-yl) benzene-1,3-diol (3b; entry 2): 1- (3,5-dihydroxyphenyl) ethanone (1b) as ketone As a colorless viscous liquid (yield: quant.)

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.41 (s, 3H), 2.30 (br s, 1H), 2.36 (dd, J = 8.0 Hz, J = 13.6 Hz, 1H), 2.56 (dd, J = 6.4 Hz, J = 13.6 Hz, 1H), 5.00-5.09 (m, 2H), 5.50-5.63 (m, 1H), 6.20 (t, J = 2.4 Hz, 1H), 6.41 (d, J = 2.4 Hz , 2H), 6.80 (s, 2H); ¹³ C NMR CDCl ₃ , 100 MHz): δ = 29.59, 48.14, 73.77, 101.21, 104.31, 119.33, 133.70, 150.64, 157.26; IR (neat): ν = 3276, 2978, 2255, 1602, 1445, 1338, 1268, 1159, 1048, 1025, 1000, 918, 846, 736, 704 cm ^-1 ; HRMS (ESI) calcd.for C ₁₁ H ₁₃ O ₂ ⁺ = [M-OH ] ⁺ : m / z = 177.0910, found: m / z = 177.0914.

生成物3c；2-(2-Bromophenyl)pent-4-en-2-ol (3c; entry 3): ケトンとして1-(2-bromophenyl)ethanone (1c)を用いたときに無色液体 (収率: 97%);として得られ、式VII

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 1.67 (s, 3H), 2.59 (dd, J = 8.0 Hz, J = 14.4 Hz, 1H), 2.59 (br s, 1H), 3.23 (dd, J = 6.4 Hz, J = 14.4 Hz, 1H), 5.02-5.11 (m, 2H), 5.45-5.55 (m, 1H), 7.04 (dt, J = 1.6 Hz, J = 7.6 Hz, 1H), 7.20-7.28 (m, 1H), 7.52 (dd, J = 0.8 Hz, J = 7.6 Hz, 1H), 7.64 (dd, J = 1.6 Hz, J = 7.6 Hz, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ= 27.27, 45.02, 74.60, 119.32, 119.93, 127.37, 128.22, 128.51, 133.58, 135.00, 144.96; IR (neat): ν = 3464, 3073, 2977, 2932, 1639, 1562, 1463, 1432, 1375, 1345, 1270, 1016, 919, 864, 758, 739, 723 cm^-1; HRMS (ESI) calcd. for C₁₁H₁₂Br⁺ = [M-OH]⁺: m/z = 223.0117, found: m/z = 223.0114. Product 3c; 2- (2-Bromophenyl) pent-4-en-2-ol (3c; entry 3): colorless liquid when 1- (2-bromophenyl) ethanone (1c) is used as the ketone (yield) : 97%); obtained as formula VII

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.67 (s, 3H), 2.59 (dd, J = 8.0 Hz, J = 14.4 Hz, 1H), 2.59 (br s, 1H), 3.23 (dd, J = 6.4 Hz, J = 14.4 Hz, 1H), 5.02-5.11 (m, 2H), 5.45-5.55 (m, 1H), 7.04 (dt, J = 1.6 Hz, J = 7.6 Hz, 1H), 7.20-7.28 (m, 1H), 7.52 (dd, J = 0.8 Hz, J = 7.6 Hz, 1H), 7.64 (dd, J = 1.6 Hz, J = 7.6 Hz, 1H); ¹³ C NMR (CDCl ₃ , 100 MHz) : δ = 27.27, 45.02, 74.60, 119.32, 119.93, 127.37, 128.22, 128.51, 133.58, 135.00, 144.96; IR (neat): ν = 3464, 3073, 2977, 2932, 1639, 1562, 1463, 1432, 1375, 1345, 1270, 1016, 919, 864, 758, 739, 723 cm ^-1 ; HRMS (ESI) calcd. For C ₁₁ H ₁₂ Br ⁺ = [M-OH] ⁺ : m / z = 223.0117, found: m / z = 223.0114.

生成物3d；2-(4-Aminophenyl)pent-4-en-2-ol (3d; entry 4): ケトンとして1-(4-aminophenyl)ethanone (1d)を用いたときに淡黄色粘性液体 (収率: 99%)として得られ、式VIII

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 1.43 (s, 3H), 1.88 (br s, 1H), 2.39 (dd, J = 8.4 Hz, J = 13.6 Hz, 1H), 2.57 (dd, J = 6.4 Hz, J = 13.6 Hz, 1H), 3.57 (br s, 2H), 4.98-5.08 (m, 2H), 5.51-5.64 (m, 1H), 6.59 (d, J = 8.8 Hz, 2H), 7.15 (d, J = 8.8 Hz, 2H); ¹³C NMR (CDCl₃, 100 MHz): δ= 29.82, 48.49, 73.36, 114.81, 119.07, 125.81, 134.06, 137.82, 144.91; IR (neat): ν = 3357, 2976, 2928, 1620, 1517, 1434, 1373, 1268, 1183, 1074, 999, 916, 830, 737 cm^-1; HRMS (ESI) calcd. for C₁₁H₁₆NO⁺ = [M+H]⁺: m/z = 178.1226, found: m/z = 178.1226. Product 3d; 2- (4-Aminophenyl) pent-4-en-2-ol (3d; entry 4): A pale yellow viscous liquid when 1- (4-aminophenyl) ethanone (1d) is used as the ketone ( (Yield: 99%)

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.43 (s, 3H), 1.88 (br s, 1H), 2.39 (dd, J = 8.4 Hz, J = 13.6 Hz, 1H), 2.57 (dd, J = 6.4 Hz, J = 13.6 Hz, 1H), 3.57 (br s, 2H), 4.98-5.08 (m, 2H), 5.51-5.64 (m, 1H), 6.59 (d, J = 8.8 Hz, 2H), 7.15 (d, J = 8.8 Hz, 2H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 29.82, 48.49, 73.36, 114.81, 119.07, 125.81, 134.06, 137.82, 144.91; IR (neat): ν = 3357, 2976, 2928, 1620, 1517, 1434, 1373, 1268, 1183, 1074, 999, 916, 830, 737 cm ^-1 ; HRMS (ESI) calcd. For C ₁₁ H ₁₆ NO ⁺ = [M + H] ⁺ : m / z = 178.1226, found: m / z = 178.1226.

生成物3e；2-(4-Nitrophenyl)pent-4-en-2-ol³ (3e; entry 5): ケトンとして1-(4-nitrophenyl)ethanone (1e)を用いたときに淡黄色液体 (収率: 91%)として得られ、式IX

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 1.55 (s, 3H), 2.17 (s, 1H), 2.51 (dd, J = 8.4 Hz, J = 13.6 Hz, 1H), 2.65 (dd, J = 6.4 Hz, J = 13.6 Hz, 1H), 5.10-5.15 (m, 2H), 5.51-5.62 (m, 1H), 7.59 (d, J = 9.2 Hz, 1H), 8.17 (d, J = 9.2 Hz, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ= 29.82, 48.23, 73.64, 120.55, 123.42, 125.89, 132.42, 146.73, 155.00; IR (neat): ν = 3542, 3077, 2979, 2932, 1640, 1603, 1519, 1454, 1409, 1349, 1109, 1069, 1013, 998, 922, 854, 757, 741, Product 3e; 2- (4-Nitrophenyl) pent-4-en-2-ol ³ (3e; entry 5): a pale yellow liquid when 1- (4-nitrophenyl) ethanone (1e) is used as the ketone ( Yield: 91%), formula IX

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.55 (s, 3H), 2.17 (s, 1H), 2.51 (dd, J = 8.4 Hz, J = 13.6 Hz, 1H), 2.65 (dd, J = 6.4 Hz, J = 13.6 Hz, 1H), 5.10-5.15 (m, 2H), 5.51-5.62 (m, 1H), 7.59 (d, J = 9.2 Hz, 1H), 8.17 (d, J = 9.2 Hz, ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 29.82, 48.23, 73.64, 120.55, 123.42, 125.89, 132.42, 146.73, 155.00; IR (neat): ν = 3542, 3077, 2979, 2932, 1640 , 1603, 1519, 1454, 1409, 1349, 1109, 1069, 1013, 998, 922, 854, 757, 741,

生成物3f；2-(Naphthalen-1-yl)pent-4-en-2-ol (3f; entry 6): ケトンとして1-(naphthalen-4-yl)ethanone (1f)を用いたときに白色固体 (収率: quant.)として得られ、式X

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 1.73 (s, 3H), 2.22 (s, 1H), 2.73 (dd, J = 7.6 Hz, J = 14.0 Hz, 1H), 3.02 (dd, J = 6.8 Hz, J = 14.0 Hz, 1H), 5.00-5.07 (m, 2H), 5.52-5.62 (m, 1H), 7.30-7.43 (m, 4H), 7.49 (d, J = 7.6 Hz, 1H), 7.68 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 8.65 (d, J = 8.4 Hz, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ= 29.59, 47.20, 75.21, 119.24, 123.65, 124.75, 125.09, 125.29, 126.77, 128.56, 129.18, 130.77, 133.88, 134.88, 142.13; IR (KBr): ν = 3242, 2973, 1639, 1599, 1508, 1449, 1366, 1273, 1130, 1103, 1065, 1022, 993, 935, 913, 874, 806, 779 cm^-1; HRMS (ESI) calcd. for C₁₅H₁₅ ⁺ = [M-OH]⁺: m/z = 195.1168, found: m/z = 195.1161. Product 3f; 2- (Naphthalen-1-yl) pent-4-en-2-ol (3f; entry 6): white when 1- (naphthalen-4-yl) ethanone (1f) is used as the ketone Obtained as a solid (yield: quant.)

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.73 (s, 3H), 2.22 (s, 1H), 2.73 (dd, J = 7.6 Hz, J = 14.0 Hz, 1H), 3.02 (dd, J = 6.8 Hz, J = 14.0 Hz, 1H), 5.00-5.07 (m, 2H), 5.52-5.62 (m, 1H), 7.30-7.43 (m, 4H), 7.49 (d, J = 7.6 Hz, 1H), 7.68 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 8.65 (d, J = 8.4 Hz, 1H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 29.59 , 47.20, 75.21, 119.24, 123.65, 124.75, 125.09, 125.29, 126.77, 128.56, 129.18, 130.77, 133.88, 134.88, 142.13; IR (KBr): ν = 3242, 2973, 1639, 1599, 1508, 1449, 1366, 1273, 1130, 1103, 1065, 1022, 993, 935, 913, 874, 806, 779 cm ^-1 ; HRMS (ESI) calcd.for C ₁₅ H ₁₅ ⁺ = [M-OH] ⁺ : m / z = 195.1168 , found: m / z = 195.1161.

生成物3g；2-(Naphthalen-2-yl)pent-4-en-2-ol² (3g; entry 7): ケトンとして1-(naphthalen-3-yl)ethanone (1g)を用いたときに淡黄色液体 (収率: 98%)として得られ、式XI

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 1.54 (s, 3H), 2.13 (s, 1H), 2.50 (dd, J = 8.0 Hz, J = 13.6 Hz, 1H), 2.71 (dd, J = 6.4 Hz, J = 13.6 Hz, 1H), 5.01-5.09 (m, 2H), 5.48-5.58 (m, 1H), 7.34-7.46 (m, 3H), 7.72-7.76 (m, 3H), 7.83 (s, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ= 29.90, 48.25, 73.77, 119.55, 123.18, 123.52, 125.67, 126.03, 127.44, 127.87, 128.12, 132.22, 133.14, 133.57, 144.95; IR (neat): ν = 3450, 3060, 2979, 2932, 1638, 1601, 1506, 1435, 1376, 1272, 1131, 998, 911, 857, 819, 748, 478 cm^-1; HRMS (ESI) calcd. for C₁₅H₁₅ ⁺ = [M-OH]⁺: m/z = 195.1168, found: m/z = 195.1163. Product 3g; 2- (Naphthalen-2-yl) pent-4-en-2-ol ² (3g; entry 7): When 1- (naphthalen-3-yl) ethanone (1g) is used as the ketone Obtained as a pale yellow liquid (yield: 98%) and has the formula XI

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.54 (s, 3H), 2.13 (s, 1H), 2.50 (dd, J = 8.0 Hz, J = 13.6 Hz, 1H), 2.71 (dd, J = 6.4 Hz, J = 13.6 Hz, 1H), 5.01-5.09 (m, 2H), 5.48-5.58 (m, 1H), 7.34-7.46 (m, 3H), 7.72-7.76 (m, 3H), 7.83 (s , 1H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 29.90, 48.25, 73.77, 119.55, 123.18, 123.52, 125.67, 126.03, 127.44, 127.87, 128.12, 132.22, 133.14, 133.57, 144.95; IR (neat ): ν = 3450, 3060, 2979, 2932, 1638, 1601, 1506, 1435, 1376, 1272, 1131, 998, 911, 857, 819, 748, 478 cm ^-1 ; HRMS (ESI) calcd.for C ₁₅ H ₁₅ ⁺ = [M-OH] ⁺ : m / z = 195.1168, found: m / z = 195.1163.

生成物3h；(E)-3-Methyl-1-phenylhexa-1,5-dien-3-ol (3h; entry 8): ケトンとして(E)-4-phenylbut-3-en-2-one (1h)を用いたときに淡黄色液体 (収率: quant.)として得られ、式XII

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 1.31 (s, 3H), 1.75 (s, 1H), 2.28 (dd, J = 8.0 Hz, J = 13.6 Hz, 1H), 2.37 (dd, J = 6.4 Hz, J = 13.6 Hz, 1H), 5.07-5.11 (m, 2H), 5.71-5.82 (m, 1H), 6.22 (d, J = 16.0 Hz, 1H), 6.52 (d, J = 16.0 Hz, 1H), 7.13-7.32 (m, 5H); ¹³C NMR (CDCl₃, 100 MHz): δ= 27.95, 47.30, 72.31, 119.31, 126.39, 127.38, 128.53, 133.53, 136.18, 136.87; IR (neat): ν = 3399, 3078, 3026, 2976, 2928, 1639, 1599, 1494, 1447, 1372, 1273, 1101, 970, 917, 851, 792, 748, 693, 599, 531 cm^-1; HRMS (ESI) calcd. for C₁₃H₁₅ ⁺ = [M-OH]⁺: m/z = 171.1168, found: m/z = 171.1162. Product 3h; (E) -3-Methyl-1-phenylhexa-1,5-dien-3-ol (3h; entry 8): (E) -4-phenylbut-3-en-2-one ( 1h) is obtained as a pale yellow liquid (yield: quant.) And has the formula XII

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.31 (s, 3H), 1.75 (s, 1H), 2.28 (dd, J = 8.0 Hz, J = 13.6 Hz, 1H), 2.37 (dd, J = 6.4 Hz, J = 13.6 Hz, 1H), 5.07-5.11 (m, 2H), 5.71-5.82 (m, 1H), 6.22 (d, J = 16.0 Hz, 1H), 6.52 (d, J = 16.0 Hz, 1H), 7.13-7.32 (m, 5H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 27.95, 47.30, 72.31, 119.31, 126.39, 127.38, 128.53, 133.53, 136.18, 136.87; IR (neat): ν = 3399, 3078, 3026, 2976, 2928, 1639, 1599, 1494, 1447, 1372, 1273, 1101, 970, 917, 851, 792, 748, 693, 599, 531 cm ^-1 ; HRMS (ESI) calcd for C ₁₃ H ₁₅ ⁺ = [M-OH] ⁺ : m / z = 171.1168, found: m / z = 171.1162.

生成物3i；4-(3-Hydroxyhex-5-en-3-yl)phenol (3i; entry 9): ケトンとして1-(4-hydroxyphenyl)propan-1-one (1i)を用いたときに白色固体 (収率: 98%)として得られ、式XIII

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 0.74 (t, J = 7.6 Hz, 3H), 1.79 (dq, J = 3.6 Hz, J = 7.6 Hz, 2H), 1.97 (s, 1H), 2.45 (dd, J = 8.4 Hz, J = 13.6 Hz, 1H), 2.67 (dd, J = 6.0 Hz, J = 13.6 Hz, 1H), 5.06-5.14 (m, 2H), 5.51-5.63 (m, 1H), 5.86 (br s, 1H), 6.79 (d, J = 8.8 Hz, 2H), 7.23 (d, J = 8.8 Hz, 2H); ¹³C NMR (CDCl₃, 100 MHz): δ= 7.84, 35.21, 46.79, 75.91, 114.83, 119.52, 126.76, 133.60, 137.91, 154.08; IR (KBr): ν = 3219, 2935, 1609, 1574, 1513, 1436, 1359, 1286, 1257, 1228, 1174, 1019, 915, 880, 831, 735 cm^-1; HRMS (ESI) calcd. for C₁₂H₁₅O⁺ = [M-OH]⁺: m/z = 175.1117, found: m/z = 175.1113. Product 3i; 4- (3-Hydroxyhex-5-en-3-yl) phenol (3i; entry 9): white when 1- (4-hydroxyphenyl) propan-1-one (1i) is used as the ketone Obtained as a solid (yield: 98%), formula XIII

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 0.74 (t, J = 7.6 Hz, 3H), 1.79 (dq, J = 3.6 Hz, J = 7.6 Hz, 2H), 1.97 (s, 1H), 2.45 (dd, J = 8.4 Hz, J = 13.6 Hz, 1H), 2.67 (dd, J = 6.0 Hz, J = 13.6 Hz, 1H), 5.06-5.14 (m, 2H), 5.51-5.63 (m, 1H) , 5.86 (br s, 1H), 6.79 (d, J = 8.8 Hz, 2H), 7.23 (d, J = 8.8 Hz, 2H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 7.84, 35.21, 46.79, 75.91, 114.83, 119.52, 126.76, 133.60, 137.91, 154.08; IR (KBr): ν = 3219, 2935, 1609, 1574, 1513, 1436, 1359, 1286, 1257, 1228, 1174, 1019, 915, 880 , 831, 735 cm ^-1 ; HRMS (ESI) calcd.for C ₁₂ H ₁₅ O ⁺ = [M-OH] ⁺ : m / z = 175.1117, found: m / z = 175.1113.

生成物3j；3-(4-Chlorophenyl)hex-5-en-3-ol (3j; entry 10):ケトンとして1-(4-chlorophenyl)propan-1-one (1j)を用いたときに淡黄色液体 (収率: 99%)として得られ、式XIV

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 0.68 (t, J = 7.6 Hz, 3H), 1.74 (dq, J = 3.6 Hz, J = 7.6 Hz, 2H), 1.90 (s, 1H), 2.41 (dd, J = 8.8 Hz, J = 13.6 Hz, 1H), 2.60 (dd, J = 6.4 Hz, J = 13.6 Hz, 1H), 5.04-5.08 (m, 2H), 5.43-5.53 (m, 1H), 7.21-7.27 (m, 4H); ¹³C NMR (CDCl₃, 100 MHz): δ= 7.71, 35.21, 46.88, 75.74, 119.91, 126.94, 128.14, 132.22, 133.11, 144.29; IR (neat): ν = 3451, 3115, 2979, 1639, 1490, 1462, 1094, 1013, 981, 919, 877, 829, 753, 590, 414 cm^-1; HRMS (ESI) calcd. for C₁₂H₁₄Cl⁺ = [M-OH]⁺: m/z = 193.0779, found: m/z = 193.0780. Product 3j; 3- (4-Chlorophenyl) hex-5-en-3-ol (3j; entry 10): light when 1- (4-chlorophenyl) propan-1-one (1j) is used as the ketone Obtained as a yellow liquid (yield: 99%), formula XIV

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 0.68 (t, J = 7.6 Hz, 3H), 1.74 (dq, J = 3.6 Hz, J = 7.6 Hz, 2H), 1.90 (s, 1H), 2.41 (dd, J = 8.8 Hz, J = 13.6 Hz, 1H), 2.60 (dd, J = 6.4 Hz, J = 13.6 Hz, 1H), 5.04-5.08 (m, 2H), 5.43-5.53 (m, 1H) , 7.21-7.27 (m, 4H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 7.71, 35.21, 46.88, 75.74, 119.91, 126.94, 128.14, 132.22, 133.11, 144.29; IR (neat): ν = 3451, 3115, 2979, 1639, 1490, 1462, 1094, 1013, 981, 919, 877, 829, 753, 590, 414 cm ^-1 ; HRMS (ESI) calcd.for C ₁₂ H ₁₄ Cl ⁺ = [M- OH] ⁺ : m / z = 193.0779, found: m / z = 193.0780.

生成物3k；4-(4-Chlorophenyl)hept-1-en-4-ol (3k; entry 11):ケトンとして1-(4-chlorophenyl)butan-1-one (1k)を用いたときに淡黄色液体 (収率: 90%)として得られ、式XV

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 0.77 (t, J = 7.6 Hz, 3H), 0.91-1.02 (m, 1H), 1.20-1.29 (m, 1H), 1.62-1.74 (m, 2H), 1.92 (s, 1H), 2.40 (dd, J = 8.4 Hz, J = 14.0 Hz, 1H), 2.60 (dd, J = 6.4 Hz, J = 14.0 Hz, 1H), 5.03-5.08 (m, 2H), 5.42-5.52 (m, 1H), 7.21-7.26 (m, 4H); ¹³C NMR (CDCl₃, 100 MHz): δ= 14.33, 16.69, 44.99, 47.27, 75.57, 119.96, 126.83, 128.15, 132.18, 133.08, 144.65; IR (neat): ν = 3467, 3077, 2959, 2872, 1639, 1490, 1456, 1399, 1093, 1013, 968, 919, 830, 757, 619 cm^-1; HRMS (ESI) calcd. for C₁₃H₁₆Cl⁺ = [M-OH]⁺: m/z = 207.0935, found: m/z = 207.0940. Product 3k; 4- (4-Chlorophenyl) hept-1-en-4-ol (3k; entry 11): light when 1- (4-chlorophenyl) butan-1-one (1k) is used as the ketone Obtained as a yellow liquid (yield: 90%), formula XV

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 0.77 (t, J = 7.6 Hz, 3H), 0.91-1.02 (m, 1H), 1.20-1.29 (m, 1H), 1.62-1.74 (m, 2H ), 1.92 (s, 1H), 2.40 (dd, J = 8.4 Hz, J = 14.0 Hz, 1H), 2.60 (dd, J = 6.4 Hz, J = 14.0 Hz, 1H), 5.03-5.08 (m, 2H ), 5.42-5.52 (m, 1H), 7.21-7.26 (m, 4H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 14.33, 16.69, 44.99, 47.27, 75.57, 119.96, 126.83, 128.15, 132.18 , 133.08, 144.65; IR (neat): ν = 3467, 3077, 2959, 2872, 1639, 1490, 1456, 1399, 1093, 1013, 968, 919, 830, 757, 619 cm ^-1 ; HRMS (ESI) calcd for C ₁₃ H ₁₆ Cl ⁺ = [M-OH] ⁺ : m / z = 207.0935, found: m / z = 207.0940.

生成物3l；1,1-Diphenylbut-3-en-1-ol (3l; entry 12):ケトンとしてbenzophenone (1l)を用いたときに無色粘性液体 (収率: 99%)として得られ、式XVI

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 2.47 (s, 1H), 3.00 (d, J = 7.2 Hz, 2H), 5.08-5.18 (m, 1H), 5.53-5.64 (m, 1H), 7.11-7.38 (m, 10H); ¹³C NMR (CDCl₃, 100 MHz): δ= 46.67, 76.85, 120.46, 125.95, 126.84, 128.14, 133.40, 1146.48; IR (neat): ν = 3456, 3063, 1638, 1599, 1494, 1447, 1347, 1167, 1054, 991, 911, 754, 730, 700, 670, 621, 573 cm^-1; HRMS (ESI) calcd. for C₁₆H₁₅ ⁺ = [M-OH]⁺: m/z = 207.1168, found: m/z = 207.1164. Product 3l; 1,1-Diphenylbut-3-en-1-ol (3l; entry 12): obtained as a colorless viscous liquid (yield: 99%) when benzophenone (1l) is used as the ketone. XVI

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 2.47 (s, 1H), 3.00 (d, J = 7.2 Hz, 2H), 5.08-5.18 (m, 1H), 5.53-5.64 (m, 1H), 7.11-7.38 (m, 10H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 46.67, 76.85, 120.46, 125.95, 126.84, 128.14, 133.40, 1146.48; IR (neat): ν = 3456, 3063, 1638 , 1599, 1494, 1447, 1347, 1167, 1054, 991, 911, 754, 730, 700, 670, 621, 573 cm ^-1 ; HRMS (ESI) calcd. For C ₁₆ H ₁₅ ⁺ = [M-OH] ⁺ : m / z = 207.1168, found: m / z = 207.1164.

生成物3m；1-Allyl-2,3-dihydro-5-methoxy-1H-inden-1-ol (3m; Tentry 13):ケトンとして2,3-dihydro-5-methoxyinden-1-one (1m)を用いたときに淡黄色液体 (収率: 81%)として得られ、式XVII

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 1.98 (br s, 1H), 2.05-2.16 (m, 1H), 2.29-2.40 (m, 1H), 2.53 (dd, J = 6.8 Hz, J = 13.6 Hz, 1H), 2.65 (dd, J = 7.6 Hz, J = 13.6 Hz, 1H), 2.74-2.85 (m, 1H), 2.94-3.05 (m, 1H), 3.81 (s, 3H), 5.13-5.22 (m, 2H), 5.79-5.94 (m, 1H), 6.76-6.84 (m, 2H), 7.27 (d, J = 6.4 Hz, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ= 29.48, 39.95, 45.15, 55.38, 82.25, 109.76, 112.89, 118.657, 123.63, 133.93, 139.29, 144.85, 160.11; IR (neat): ν = 3419, 3073, 2939, 2835, 1606, 1491, 1435, 1305, 1255, 1144, 1102, 1033, 998, 917, 845, 821, 738 cm^-1; HRMS (ESI) calcd. for C₁₃H₁₅O⁺ = [M-OH]⁺: m/z = 187.1117, found: m/z = 187.1116. Product 3m; 1-Allyl-2,3-dihydro-5-methoxy-1H-inden-1-ol (3m; Tentry 13): 2,3-dihydro-5-methoxyinden-1-one (1m) as a ketone Is obtained as a pale yellow liquid (yield: 81%) and has the formula XVII

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.98 (br s, 1H), 2.05-2.16 (m, 1H), 2.29-2.40 (m, 1H), 2.53 (dd, J = 6.8 Hz, J = 13.6 Hz, 1H), 2.65 (dd, J = 7.6 Hz, J = 13.6 Hz, 1H), 2.74-2.85 (m, 1H), 2.94-3.05 (m, 1H), 3.81 (s, 3H), 5.13- 5.22 (m, 2H), 5.79-5.94 (m, 1H), 6.76-6.84 (m, 2H), 7.27 (d, J = 6.4 Hz, 1H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 29.48, 39.95, 45.15, 55.38, 82.25, 109.76, 112.89, 118.657, 123.63, 133.93, 139.29, 144.85, 160.11; IR (neat): ν = 3419, 3073, 2939, 2835, 1606, 1491, 1435, 1305, 1255 , 1144, 1102, 1033, 998, 917, 845, 821, 738 cm ^-1 ; HRMS (ESI) calcd.for C ₁₃ H ₁₅ O ⁺ = [M-OH] ⁺ : m / z = 187.1117, found: m / z = 187.1116.

生成物3n；1-Allyl-2,3-dihydro-6-methyl-1H-inden-1-ol (3n; entry 14):ケトンとして2,3-dihydro-6-methylinden-1-one (1n)を用いたときに無色液体 (収率: 85%)として得られ、式XVIII

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 1.98-2.09 (m, 1H), 2.00 (s, 1H), 2.28-2.37 (m, 2H), 2.35 (s, 3H), 2.49 (dd, J = 6.8 Hz, J = 13.6 Hz, 1H), 2.61 (dd, J = 8.0 Hz, J = 13.6 Hz, 1H), 2.71-2.79 (m, 1H), 2.90-2.97 (m, 2H), 5.13-5.18 (m, 2H), 5.79-5.90 (m, 1H), 7.05-7.13 (m, 3H); ¹³C NMR (CDCl₃, 100 MHz): δ= 21.33, 28.97, 39.87, 44.94, 82.62, 118.75, 123.33, 124.62, 129.13, 133.83, 136.28, 139.94, 147.14; IR (neat): ν = 3387, 3075, 3008, 2925, 2854, 2246, 1639, 1493, 1440, 1319, 1265, 1168, 1054, 997, 911, 816, 735 cm^-1; HRMS (ESI) calcd. for C₁₃H₁₅ ⁺ = [M-OH]⁺: m/z = 171.1168, found: m/z = 171.1166. Product 3n; 1-Allyl-2,3-dihydro-6-methyl-1H-inden-1-ol (3n; entry 14): 2,3-dihydro-6-methylinden-1-one (1n) as a ketone Is obtained as a colorless liquid (yield: 85%) and has the formula XVIII

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.98-2.09 (m, 1H), 2.00 (s, 1H), 2.28-2.37 (m, 2H), 2.35 (s, 3H), 2.49 (dd, J = 6.8 Hz, J = 13.6 Hz, 1H), 2.61 (dd, J = 8.0 Hz, J = 13.6 Hz, 1H), 2.71-2.79 (m, 1H), 2.90-2.97 (m, 2H), 5.13-5.18 (m, 2H), 5.79-5.90 (m, 1H), 7.05-7.13 (m, 3H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 21.33, 28.97, 39.87, 44.94, 82.62, 118.75, 123.33 , 124.62, 129.13, 133.83, 136.28, 139.94, 147.14; IR (neat): ν = 3387, 3075, 3008, 2925, 2854, 2246, 1639, 1493, 1440, 1319, 1265, 1168, 1054, 997, 911, 816, 735 cm ^-1 ; HRMS (ESI) calcd.for C ₁₃ H ₁₅ ⁺ = [M-OH] ⁺ : m / z = 171.1168, found: m / z = 171.1166.

生成物3o；1-Allyl-1,2,3,4-tetrahydro-6-methoxynaphthalen-1-ol (3o; entry 15):ケトンとして3,4-dihydro-6-methoxynaphthalen-1(2H)-one (1o)を用いたときに淡黄色液体 (収率: 70%);として得られ、式XIX

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 1.71-2.04 (m, 4H), 1.91 (br s, 1H), 2.58 (d, J = 7.2 Hz, 2H), 2.63-2.82 (m, 2H), 3.76 (s, 3H), 5.06-5.14 (m, 2H), 5.70-5.84 (m, 1H), 6.58 (d, J = 2.8 Hz, 1H), 6.76 (dd, J = 2.8 Hz, J = 8.8 Hz, 1H), 7.45 (d, J = 8.8 Hz, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ= 19.70, 30.18, 36.24, 47.07, 55.12, 71.58, 112.55, 113.02, 118.39, 127.71, 134.10, 134.20, 138.39, 158.39; IR (neat): ν = 3433, 3072, 2935, 2835, 1608, 1576, 1499, 1444, 1320, 1254, 1159, 1127, 1039, 1011, 970, 914, 836, 743 cm^-1; HRMS (ESI) calcd. for C₁₄H₁₇O⁺ = [M-OH]⁺: m/z = 201.1274, found: m/z = 201.1272. Product 3o; 1-Allyl-1,2,3,4-tetrahydro-6-methoxynaphthalen-1-ol (3o; entry 15): 3,4-dihydro-6-methoxynaphthalen-1 (2H) -one as a ketone (1o) was obtained as a pale yellow liquid (yield: 70%);

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.71-2.04 (m, 4H), 1.91 (br s, 1H), 2.58 (d, J = 7.2 Hz, 2H), 2.63-2.82 (m, 2H) , 3.76 (s, 3H), 5.06-5.14 (m, 2H), 5.70-5.84 (m, 1H), 6.58 (d, J = 2.8 Hz, 1H), 6.76 (dd, J = 2.8 Hz, J = 8.8 Hz, 1H), 7.45 (d, J = 8.8 Hz, 1H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 19.70, 30.18, 36.24, 47.07, 55.12, 71.58, 112.55, 113.02, 118.39, 127.71, 134.10, 134.20, 138.39, 158.39; IR (neat): ν = 3433, 3072, 2935, 2835, 1608, 1576, 1499, 1444, 1320, 1254, 1159, 1127, 1039, 1011, 970, 914, 836, 743 cm ^-1 ; HRMS (ESI) calcd.for C ₁₄ H ₁₇ O ⁺ = [M-OH] ⁺ : m / z = 201.1274, found: m / z = 201.1272.

生成物3p；1-Allylcyclohexanol (3p; entry 16):ケトンとしてcyclohexanone (1p)を用いたときに淡黄色液体 (収率: 90%)として得られ、式XX

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 1.15-1.61 (m, 10H), 1.80 (br s, 1H), 2.15 (d, J = 7.6 Hz, 1H), 2.34 (d, J = 7.6 Hz, 1H), 4.94-5.11 (m, 2H), 5.71-5.88 (m, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ= 21.98, 25.61, 37.03, 46.59, 71.25, 117.86, 133.75; IR (neat): ν = 3437, 3075, 2939, 2865, 1457, 1369, 1310, 1144, 1082, 1035, 911, 780 cm^-1; HRMS (ESI) calcd. for C₉H₁₅ ⁺ = [M-OH]⁺: m/z 123.1168, found: m/z 123.1169. Product 3p; 1-Allylcyclohexanol (3p; entry 16): obtained as a pale yellow liquid (yield: 90%) when cyclohexanone (1p) is used as the ketone, formula XX

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.15-1.61 (m, 10H), 1.80 (br s, 1H), 2.15 (d, J = 7.6 Hz, 1H), 2.34 (d, J = 7.6 Hz , 1H), 4.94-5.11 (m, 2H), 5.71-5.88 (m, 1H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 21.98, 25.61, 37.03, 46.59, 71.25, 117.86, 133.75; IR (neat): ν = 3437, 3075, 2939, 2865, 1457, 1369, 1310, 1144, 1082, 1035, 911, 780 cm ^-1 ; HRMS (ESI) calcd.for C ₉ H ₁₅ ⁺ = [M-OH ] ⁺ : m / z 123.1168, found: m / z 123.1169.

生成物3q；1-Allyl-4-phenylcyclohexanol (3q; entry 17):ケトンとして4-phenylcyclohexanone (1q)を用いたときにMajor diastereoisomerが淡黄色液体 (収率: 61%)として得られ、式XXI

で表されるものであった。
Major diastereoisomer;¹H NMR (CDCl₃, 400 MHz): δ= 1.36 (s, 1H), 1.46-1.56 (m, 2H), 1.67-1.78 (m, 4H), 1.79-1.92 (m, 2H), 2.40 (d, J = 7.6 Hz, 2H), 2.46 (tt, J = 3.2 Hz, J = 12.4 Hz, 1H), 5.10-5.19 (m, 2H), 5.85-5.98 (m, 1H), 7.13-7.32 (m, 5H); ¹³C NMR (CDCl₃, 100 MHz): δ= 29.24, 37.24, 44.03, 48.60, 69.94, 119.01, 125.93, 126.85, 128.31, 133.53, 147.20; IR (neat): ν = 3419, 3074, 3026, 2926, 2859, 1638, 1602, 1494, 1443, 1219, 1144, 1029, 1001, 975, 914, 868, 757, 699, 533 cm^-1; HRMS (ESI) calcd. for C₁₅H₁₉ ⁺ = [M-OH]⁺: m/z = 199.1481, found: m/z = 199.1473;
Minor diastereoisomer: 白色固体 (収率: 11%); ¹H NMR (CDCl₃, 400 MHz): δ= 1.51-1.66 (m, 5H), 1.77-1.92 (m, 4H), 2.41 (d, J = 7.2 Hz, 2H), 2.51-2.62 (m, 1H), 5.12-5.22 (m, 2H), 5.83-5.97 (m, 1H), 7.14-7.32 (m, 5H); ¹³C NMR (CDCl₃, 100 MHz): δ= 30.93, 38.18, 41.31, 43.39, 71.35, 119.17, 126.08, 126.79, 128.37, 133.40, 146.35; IR (KBr):ν = 3315, 3025, 2923, 2860, 1637, 1493, 1451, 1429, 1227, 1136, 1030, 998, 904, 877, 760, 703 cm^-1; HRMS (ESI) calcd. for C₁₅H₁₉ ⁺ = [M-OH]⁺: m/z = 199.1481, found: m/z = 199.1483. Product 3q; 1-Allyl-4-phenylcyclohexanol (3q; entry 17): Major diastereoisomer is obtained as a pale yellow liquid (yield: 61%) when 4-phenylcyclohexanone (1q) is used as the ketone, and has the formula XXI

It was represented by.
Major diastereoisomer; ¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.36 (s, 1H), 1.46-1.56 (m, 2H), 1.67-1.78 (m, 4H), 1.79-1.92 (m, 2H), 2.40 (d, J = 7.6 Hz, 2H), 2.46 (tt, J = 3.2 Hz, J = 12.4 Hz, 1H), 5.10-5.19 (m, 2H), 5.85-5.98 (m, 1H), 7.13-7.32 (m, 5H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 29.24, 37.24, 44.03, 48.60, 69.94, 119.01, 125.93, 126.85, 128.31, 133.53, 147.20; IR (neat): ν = 3419, 3074, 3026, 2926, 2859, 1638, 1602, 1494, 1443, 1219, 1144, 1029, 1001, 975, 914, 868, 757, 699, 533 cm ^-1 ; HRMS (ESI) calcd.for C ₁₅ H ₁₉ ⁺ = [M-OH] ⁺ : m / z = 199.1481, found: m / z = 199.1473;
Minor diastereoisomer: White solid (Yield: 11%); ¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.51-1.66 (m, 5H), 1.77-1.92 (m, 4H), 2.41 (d, J = 7.2 Hz, 2H), 2.51-2.62 (m, 1H), 5.12-5.22 (m, 2H), 5.83-5.97 (m, 1H), 7.14-7.32 (m, 5H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 30.93, 38.18, 41.31, 43.39, 71.35, 119.17, 126.08, 126.79, 128.37, 133.40, 146.35; IR (KBr): ν = 3315, 3025, 2923, 2860, 1637, 1493, 1451, 1429, 1227, 1136, 1030, 998, 904, 877, 760, 703 cm ^-1 ; HRMS (ESI) calcd.for C ₁₅ H ₁₉ ⁺ = [M-OH] ⁺ : m / z = 199.1481, found: m / z = 199.1483.

生成物3r；1-Allylcyclohex-2-enol (3r; entry 18):ケトンとしてcyclohex-2-enone (1r)を用いたときに淡黄色液体(収率: 70%)として得られ、式XXII

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ=1.60-1.72 (m, 4H), 1.81-2.04 (m, 3H), 2.23 (d, J = 7.6 Hz, 2H), 4.98-5.10 (m, 2H), 5.55 (d, J = 10.4 Hz, 1H), 5.71-5.87 (m, 2H); ¹³C NMR (CDCl₃, 100 MHz): δ=18.72, 24.84, 35.11, 46.49, 68.85, 118.05, 129.73, 131.89, 133.47; IR (neat): ν = 3445, 3070, 2942, 2855, 1642, 1460, 1379, 1139, 1066, 1035, 997, 769 cm^-1; HRMS (ESI) calcd. for C₉H₁₃ ⁺ = [M-OH]⁺: m/z = 121.1012, found: m/z = 121.1010. Product 3r; 1-Allylcyclohex-2-enol (3r; entry 18): obtained as a pale yellow liquid (yield: 70%) when cyclohex-2-enone (1r) is used as the ketone, formula XXII

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.60-1.72 (m, 4H), 1.81-2.04 (m, 3H), 2.23 (d, J = 7.6 Hz, 2H), 4.98-5.10 (m, 2H ), 5.55 (d, J = 10.4 Hz, 1H), 5.71-5.87 (m, 2H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 18.72, 24.84, 35.11, 46.49, 68.85, 118.05, 129.73, 131.89, 133.47; IR (neat): ν = 3445, 3070, 2942, 2855, 1642, 1460, 1379, 1139, 1066, 1035, 997, 769 cm ^-1 ; HRMS (ESI) calcd.for C ₉ H ₁₃ ⁺ = [M-OH] ⁺ : m / z = 121.1012, found: m / z = 121.1010.

生成物3s；4-Methylnon-1-en-4-ol (3s; entry 19):ケトンとしてheptan-2-one (1s)を用いたときに淡黄色液体 (収率: 81%)として得られ、式XXIII

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ=0.87 (t, J = 6.8 Hz, 3H), 1.14 (s, 3H), 1.21-1.45 (m, 9H), 2.20 (d, J = 7.2 Hz, 2H), 5.05-5.16 (m, 2H), 5.77-5.91 (m, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ=14.04, 22.63, 23.51, 26.71, 32.37, 41.83, 46.25, 72.18, 118.59, 134.10; IR (neat): ν = 3387, 3076, 2932, 2861, 1640, 1461, 1376, 1309, 1143, 1080, 1038, 998, 913, 781 cm^-1; HRMS (ESI) calcd. for C₁₀H₁₉ ⁺ = [M-OH]⁺: m/z = 139.1481, found: m/z = 139.1479. Product 3s; 4-Methylnon-1-en-4-ol (3s; entry 19): obtained as a pale yellow liquid (yield: 81%) when heptan-2-one (1s) is used as the ketone , Formula XXIII

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 0.87 (t, J = 6.8 Hz, 3H), 1.14 (s, 3H), 1.21-1.45 (m, 9H), 2.20 (d, J = 7.2 Hz, 2H), 5.05-5.16 (m, 2H), 5.77-5.91 (m, 1H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 14.04, 22.63, 23.51, 26.71, 32.37, 41.83, 46.25, 72.18, 118.59, 134.10; IR (neat): ν = 3387, 3076, 2932, 2861, 1640, 1461, 1376, 1309, 1143, 1080, 1038, 998, 913, 781 cm ^-1 ; HRMS (ESI) calcd. For C ₁₀ H ₁₉ ⁺ = [M-OH] ⁺ : m / z = 139.1481, found: m / z = 139.1479.

生成物3t；2-(Pyridin-4-yl)pent-4-en-2-ol (3t; entry 20):ケトンとして1-(pyridin-4-yl)ethanone (1t)を用いたときに無色粘性液体 (収率: 55%)として得られ、式XIV

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ=1.47 (s, 3H), 2.43 (dd, J = 8.4 Hz, J = 14.0 Hz, 1H), 2.56 (dd, J = 6.4 Hz, J = 14.0 Hz, 1H), 2.77 (br s, 1H), 5.04-5.09 (m, 2H), 5.48-5.59 (m, 1H), 7.29 (dd, J = 1.6 Hz, J = 4.4 Hz, 2H), 8.46 (dd, J = 1.6 Hz, J = 4.4 Hz, 2H); ¹³C NMR (CDCl₃, 100 MHz): δ=29.32, 47.89, 72.94, 120.13, 132.63, 149.56, 156.73; IR (neat): ν = 3219, 2978, 2930, 1640, 1603, 1557, 1413, 1372, 1225, 1162, 1067, 1002, 917, 860, 825, 734, 655, 576 cm^-1; HRMS (ESI) calcd. for C₁₀H₁₄NO⁺ = [M+H]⁺: m/z = 164.1070, found: m/z = 164.1068. Product 3t; 2- (Pyridin-4-yl) pent-4-en-2-ol (3t; entry 20): colorless when 1- (pyridin-4-yl) ethanone (1t) is used as the ketone Obtained as a viscous liquid (yield: 55%), formula XIV

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.47 (s, 3H), 2.43 (dd, J = 8.4 Hz, J = 14.0 Hz, 1H), 2.56 (dd, J = 6.4 Hz, J = 14.0 Hz , 1H), 2.77 (br s, 1H), 5.04-5.09 (m, 2H), 5.48-5.59 (m, 1H), 7.29 (dd, J = 1.6 Hz, J = 4.4 Hz, 2H), 8.46 (dd , J = 1.6 Hz, J = 4.4 Hz, 2H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 29.32, 47.89, 72.94, 120.13, 132.63, 149.56, 156.73; IR (neat): ν = 3219, 2978, 2930, 1640, 1603, 1557, 1413, 1372, 1225, 1162, 1067, 1002, 917, 860, 825, 734, 655, 576 cm ^-1 ; HRMS (ESI) calcd.for C ₁₀ H ₁₄ NO ⁺ = [M + H] ⁺ : m / z = 164.1070, found: m / z = 164.1068.

生成物3u；2-(Furan-2-yl)pent-4-en-2-ol (3u; entry 21):ケトンとして1-(furan-2-yl)ethanone (1u)を用いたときに淡黄色液体 (収率: 92%)として得られ、式XXV

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ=1.47 (s, 3H), 2.08 (s, 1H), 2.47 (dd, J = 7.6 Hz, J = 13.6 Hz, 1H), 2.66 (dd, J = 6.8 Hz, J = 13.6 Hz, 1H), 5.04-5.09 (m, 2H), 5.56-5.66 (m, 1H), 6.13 (dd, J = 0.8 Hz, J = 3.2 Hz, 1H), 6.24 (dd, J = 1.6 Hz, J = 3.2 Hz, 1H), 7.29 (dd, J = 0.8 Hz, J = 1.6 Hz, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ=26.51, 46.13, 70.71, 104.61, 109.99, 119.18, 133.24, 141.49, 159.24; IR (neat): ν = 3433, 2980, 1571, 1469, 1360, 1288, 1161, 1102, 1012, 917, 884, 809, 737 cm^-1; HRMS (ESI) calcd. for C₉H₁₁O⁺ = [M-OH]⁺: m/z = 135.0804, found: m/z = 135.0803. Product 3u; 2- (Furan-2-yl) pent-4-en-2-ol (3u; entry 21): light when 1- (furan-2-yl) ethanone (1u) is used as the ketone Obtained as a yellow liquid (yield: 92%), formula XXV

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.47 (s, 3H), 2.08 (s, 1H), 2.47 (dd, J = 7.6 Hz, J = 13.6 Hz, 1H), 2.66 (dd, J = 6.8 Hz, J = 13.6 Hz, 1H), 5.04-5.09 (m, 2H), 5.56-5.66 (m, 1H), 6.13 (dd, J = 0.8 Hz, J = 3.2 Hz, 1H), 6.24 (dd, J = 1.6 Hz, J = 3.2 Hz, 1H), 7.29 (dd, J = 0.8 Hz, J = 1.6 Hz, 1H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 26.51, 46.13, 70.71, 104.61 , 109.99, 119.18, 133.24, 141.49, 159.24; IR (neat): ν = 3433, 2980, 1571, 1469, 1360, 1288, 1161, 1102, 1012, 917, 884, 809, 737 cm ^-1 ; HRMS (ESI ) calcd.for C ₉ H ₁₁ O ⁺ = [M-OH] ⁺ : m / z = 135.0804, found: m / z = 135.0803.

生成物3v；2-(Thiophen-2-yl)pent-4-en-2-ol(3v; entry 22):ケトンとして1-(thiophen-2-yl)ethanone (1v)を用いたときに淡黄色液体 (収率: 98%)として得られ、式XXVI

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ=1.54 (s, 3H), 2.23 (br s, 1H), 2.49 (dd, J = 7.6 Hz, J = 13.6 Hz, 1H), 2.63 (dd, J = 6.8 Hz, J = 13.6 Hz, 1H), 5.07-5.10 (m, 2H), 5.61-5.72 (m, 1H), 6.82-6.85 (m, 1H), 6.86-6.90 (m, 1H), 7.10-7.14 (m, 4H); ¹³C NMR (CDCl₃, 100 MHz): δ=30.35, 49.11, 72.89, 119.68, 122.28, 123.82, 126.69, 133.27, 153.02; IR (neat): ν = 3415, 3150, 2981, 2933, 1640, 1436, 1374, 1234, 1110, 997, 919, 831, 698 cm^-1; HRMS (ESI) calcd. for C₉H₁₁S⁺ = [M-OH]⁺: m/z = 151.0576, found: m/z = 151.0583. Product 3v; 2- (Thiophen-2-yl) pent-4-en-2-ol (3v; entry 22): light when 1- (thiophen-2-yl) ethanone (1v) is used as the ketone Obtained as a yellow liquid (yield: 98%), formula XXVI

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.54 (s, 3H), 2.23 (br s, 1H), 2.49 (dd, J = 7.6 Hz, J = 13.6 Hz, 1H), 2.63 (dd, J = 6.8 Hz, J = 13.6 Hz, 1H), 5.07-5.10 (m, 2H), 5.61-5.72 (m, 1H), 6.82-6.85 (m, 1H), 6.86-6.90 (m, 1H), 7.10- 7.14 (m, 4H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 30.35, 49.11, 72.89, 119.68, 122.28, 123.82, 126.69, 133.27, 153.02; IR (neat): ν = 3415, 3150, 2981 , 2933, 1640, 1436, 1374, 1234, 1110, 997, 919, 831, 698 cm ^-1 ; HRMS (ESI) calcd.for C ₉ H ₁₁ S ⁺ = [M-OH] ⁺ : m / z = 151.0576 , found: m / z = 151.0583.

生成物3w；2-(Thiophen-3-yl)pent-4-en-2-ol (3w; entry 23):ケトンとして1-(thiophen-3-yl)ethanone (1w)を用いたときに淡黄色液体 (収率: quant.)として得られ、式XXVII

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ=1.47 (s, 3H), 2.05 (br s, 1H), 2.42 (dd, J = 8.0 Hz, J = 13.6 Hz, 1H), 2.56 (dd, J = 6.8 Hz, J = 13.6 Hz, 1H), 5.02-5.10 (m, 2H), 5.53-5.66 (m, 1H), 6.98 (dd, J = 1.6 Hz, J = 5.2 Hz, 1H), 7.08 (dd, J = 1.6 Hz, J = 3.2 Hz, 1H), 7.21 (dd, J = 3.2 Hz, J = 5.2 Hz, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ=29.47, 48.25, 72.61, 119.32, 119.49, 125.55, 125.80, 133.57, 149.64; IR (neat): ν = 3419, 3076, 2977, 2930, 1639, 1416, 1372, 1230, 1087, 998, 918, 867, 848, 788, 683, 657 cm^-1; HRMS (ESI) calcd. for C₉H₁₁S⁺ = [M-OH]⁺: m/z = 151.0576, found: m/z = 151.0573. Product 3w; 2- (Thiophen-3-yl) pent-4-en-2-ol (3w; entry 23): light when 1- (thiophen-3-yl) ethanone (1w) is used as the ketone Obtained as a yellow liquid (yield: quant.), Formula XXVII

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.47 (s, 3H), 2.05 (br s, 1H), 2.42 (dd, J = 8.0 Hz, J = 13.6 Hz, 1H), 2.56 (dd, J = 6.8 Hz, J = 13.6 Hz, 1H), 5.02-5.10 (m, 2H), 5.53-5.66 (m, 1H), 6.98 (dd, J = 1.6 Hz, J = 5.2 Hz, 1H), 7.08 (dd , J = 1.6 Hz, J = 3.2 Hz, 1H), 7.21 (dd, J = 3.2 Hz, J = 5.2 Hz, 1H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 29.47, 48.25, 72.61, 119.32, 119.49, 125.55, 125.80, 133.57, 149.64; IR (neat): ν = 3419, 3076, 2977, 2930, 1639, 1416, 1372, 1230, 1087, 998, 918, 867, 848, 788, 683, 657 cm ^-1 ; HRMS (ESI) calcd.for C ₉ H ₁₁ S ⁺ = [M-OH] ⁺ : m / z = 151.0576, found: m / z = 151.0573.

生成物3x；3-Allyl-3-hydroxyindolin-2-one (3x; entry 24):ケトンとしてindoline-2,3-dione (1x)を用いたときに無色固体 (収率: 80%)として得られ、式XXVIII

で表されるものであった。
¹H NMR (DMSO-d₆, 400 MHz): δ=2.42 (dd, J = 8.0 Hz, J = 13.2 Hz, 1H), 2.58 (dd, J = 6.4 Hz, J = 13.2 Hz, 1H), 4.90-4.94 (m, 2H), 5.37-5.48 (m, 1H), 5.95 (br s, 1H), 6.76 (d, J = 7.6 Hz, 1H), 6.94 (t, J = 7.6 Hz, 1H), 7.17 (t, J = 7.6 Hz, 1H), 7.24 (d, J = 7.6 Hz, 1H), 10.20 (br s, 1H); ¹³C NMR (DMSO-d₆, 100 MHz): δ=42.07, 75.23, 109.41, 118.82, 121.42, 124.13, 128.85, 131.48, 131.76, 141.58, 178.71; IR (KBr): ν = 3251, 2927, 1719, 1623, 1472, 1435, 1335, 1265, 1225, 1186, 1084, 1049, 1025, 1004, 924, 822, 788, 754, 736, 701 cm^-1; HRMS (ESI) calcd. for C₁₁H₁₀NO⁺ = [M-OH]⁺: m/z = 172.0757, found: m/z = 172.0755. Product 3x; 3-Allyl-3-hydroxyindolin-2-one (3x; entry 24): obtained as a colorless solid (yield: 80%) when indoline-2,3-dione (1x) is used as the ketone Formula XXVIII

It was represented by.
¹ H NMR (DMSO-d ₆ , 400 MHz): δ = 2.42 (dd, J = 8.0 Hz, J = 13.2 Hz, 1H), 2.58 (dd, J = 6.4 Hz, J = 13.2 Hz, 1H), 4.90 -4.94 (m, 2H), 5.37-5.48 (m, 1H), 5.95 (br s, 1H), 6.76 (d, J = 7.6 Hz, 1H), 6.94 (t, J = 7.6 Hz, 1H), 7.17 (t, J = 7.6 Hz, 1H), 7.24 (d, J = 7.6 Hz, 1H), 10.20 (br s, 1H); ¹³ C NMR (DMSO-d ₆ , 100 MHz): δ = 42.07, 75.23, 109.41, 118.82, 121.42, 124.13, 128.85, 131.48, 131.76, 141.58, 178.71; IR (KBr): ν = 3251, 2927, 1719, 1623, 1472, 1435, 1335, 1265, 1225, 1186, 1084, 1049, 1025 , 1004, 924, 822, 788, 754, 736, 701 cm ^-1 ; HRMS (ESI) calcd.for C ₁₁ H ₁₀ NO ⁺ = [M-OH] ⁺ : m / z = 172.0757, found: m / z = 172.0755.

<N-ベンゾイルヒドラゾンに対する、ヨウ化インジウムによるアリル化>
セプタムキャップの付いた10 mLのフラスコにアルゴン雰囲気下、１価のヨウ化インジウム（Aldrich社、粉末、99.999%）、アシルヒドラゾン（N-ベンゾイルヒドラゾン）5(0.4 mmol、以下の文献（Kobayashi, S.; Ogawa, C.; Konishi, H.; Sugiura, M. J. Am. Chem. Soc. 2003, 125, 6610.）の方法に従って調製)を加えた。さらに乾燥したトルエン(800 μL)および乾燥したメタノール81 μL, 2.0 mmol)をN-ベンゾイルヒドラゾン5に加え、続いてピナコリルアリルボレート2(112.5 μL, 0.6 mmol)を加え、アルゴン雰囲気下、室温で撹拌した。TLCでN-ベンゾイルヒドラの消失を確認した後に塩化メチレン、飽和重曹水を加え、有機層を分離した。水層から塩化メチレンで３度抽出し、有機層を合わせて硫酸ナトリウムで乾燥し、濾過後、減圧濃縮して真空乾燥した。残渣を分取用薄層クロマトグラフィー(PTLC、ヘキサン／酢酸エチル＝９／１〜２／１)で精製し、目的物であるホモアリルヒドラジド6を得た。
反応式を式XXX

に示す。
実施例５で得られた結果を表５に示す。 <Allylation with indium iodide for N-benzoylhydrazone>
In a 10 mL flask with a septum cap, monovalent indium iodide (Aldrich, powder, 99.999%), acylhydrazone (N-benzoylhydrazone) 5 (0.4 mmol, the following reference (Kobayashi, S) Ogawa, C .; Konishi, H .; Sugiura, MJ Am. Chem. Soc. 2003, 125, 6610.). Further, dry toluene (800 μL) and dry methanol 81 μL, 2.0 mmol) were added to N-benzoylhydrazone 5, followed by pinacolylallylborate 2 (112.5 μL, 0.6 mmol), and at room temperature under an argon atmosphere at room temperature. Stir. After confirming the disappearance of N-benzoylhydra by TLC, methylene chloride and saturated aqueous sodium bicarbonate were added, and the organic layer was separated. The aqueous layer was extracted three times with methylene chloride, and the organic layers were combined, dried over sodium sulfate, filtered, concentrated under reduced pressure, and dried under vacuum. The residue was purified by preparative thin layer chromatography (PTLC, hexane / ethyl acetate = 9/1 to 2/1) to obtain homoallyl hydrazide 6 which was the target product.
Formula XXX

Shown in
The results obtained in Example 5 are shown in Table 5.

なお、表５におけるEntry1〜8は、式ＸＸＸの反応において、それぞれインジウム触媒の種類や量、及び添加剤の量を変えた場合に対応する。
表５から明らかなように、１価のヨウ化インジウム5 mol%存在下、アセトアルデヒド由来のアシルヒドラゾン（N-ベンゾイルヒドラゾン）5a、及びピナコールアリルボレートを用い、トルエン中の室温で反応を行うと、添加剤無しでは反応が進行しなかったが（entry 1）、メタノールを５当量加えると生成物であるホモアリルヒドラジ6aが高い収率で生成した（entry 3）。添加剤であるメタノールの効果としては、アシルヒドラゾンの溶解性を上げる、ピナコールアリルボレートを活性化する、触媒回転を促進するなどが考えられる。
又、インジウム触媒量を0.5 mol%に減らしても高い収率で反応が進行した（entry 4）が、インジウム触媒無しでは反応は進行せず（entry 5）、又、0価や3価のインジウム触媒を用いると収率が低下した（entry 6-8）。
なお、実施例５では溶媒としてトルエンを用いたが、他の溶媒としてテトラヒドロフラン, ジメトキシエタン、1,4-ジオキサン、ジメチルホルムアミド、アセトニトリル、ジメチルスルホキシド、水を用いることもできる。但し、本発明者らが実際に実験を行ったところ、上記他の溶媒を用いた場合、トルエンを用いた場合に比べて収率が低下したことを確認した。
このように、インジウムが触媒量でも反応が進行するのが本発明の大きな特徴であり、従来の方法、すなわちBarbier型反応やReformatsky型反応、インジウムへの金属交換反応やラジカル反応では、当量以上のインジウムが反応に必要である。 Entry 1 to 8 in Table 5 correspond to cases where the type and amount of indium catalyst and the amount of additive are changed in the reaction of formula XXX.
As apparent from Table 5, in the presence of 5 mol% of monovalent indium iodide, acylhydrazone (N-benzoylhydrazone) 5a derived from acetaldehyde and pinacol allylborate were used, and the reaction was carried out at room temperature in toluene. The reaction did not proceed without the additive (entry 1), but when 5 equivalents of methanol were added, the product homoallylhydrazide 6a was produced in a high yield (entry 3). As an effect of methanol as an additive, it is conceivable to increase the solubility of acylhydrazone, activate pinacol allyl borate, promote catalyst rotation, and the like.
The reaction proceeded with high yield even when the amount of indium catalyst was reduced to 0.5 mol% (entry 4), but without the indium catalyst, the reaction did not proceed (entry 5). The yield decreased when the catalyst was used (entry 6-8).
In Example 5, toluene was used as a solvent, but tetrahydrofuran, dimethoxyethane, 1,4-dioxane, dimethylformamide, acetonitrile, dimethyl sulfoxide, and water can also be used as other solvents. However, when the present inventors actually conducted an experiment, it was confirmed that when the other solvent was used, the yield was lower than when toluene was used.
As described above, the reaction is advanced even with a catalytic amount of indium, which is a major feature of the present invention. In the conventional methods, that is, the Barbier type reaction, the Reformatsky type reaction, the metal exchange reaction to indium and the radical reaction, the equivalent amount or more. Indium is required for the reaction.

<種々のN-アシルヒドラゾンに対する、ヨウ化インジウム触媒によるトルエン中でのアリル化>
式XXXのアシルヒドラゾン（N-ベンゾイルヒドラゾン）5の代わりに、式XXXI及び表６に示すアシルヒドラゾン7を用い、インジウム触媒としてヨウ化インジウム(I)（6.0mg;5mol%）用いたこと以外は、実施例５とまったく同様にして対応する生成物を得た。
反応式を式XXXI

に示す。
実施例６で得られた結果を表６に示す。 <Allylation in toluene with indium iodide catalyst for various N-acylhydrazones>
Instead of acyl hydrazone of formula XXX (N-benzoyl hydrazone) 5, except that the formula XXXI and the acyl hydrazone 7 shown in Table 6 were used, and indium iodide (I) (6.0 mg; 5 mol%) was used as the indium catalyst. The corresponding product was obtained exactly as in Example 5.
Reaction formula is XXXI

Shown in
The results obtained in Example 6 are shown in Table 6.

なお、表６におけるEntry1〜21は、それぞれ以下の生成物8a〜8uに対応するヒドラゾン7a〜7uと収率の組合せである。ただし、生成物8a, 8b, 8c, 8e, 8f, 8g, 8h, 8j, 8l, 8m,n,s,tは既知化合物であり、以下の報告データと同一であることを確認した。
Kobayashi, S.; Ogawa, C.; Konishi, H.; Sugiura, M. J. Am. Chem. Soc. 2003, 125, 6610.
Roush, W. R.; Adam, M. A.; Walts, A. E.; Harris, D. J. J. Am. Chem. Soc. 1986, 108, 3422.
Hirabayashi, R.; Ogawa, C.; Sugiura, M.; Kobayashi, S. J. Am. Chem. Soc. 2001,123, 9493.
Tan, K. L.; Jacobsen, E. N. Angew. Chem. Int. Ed. 2007, 46, 1315. In Table 6, Entry 1 to 21 are combinations of hydrazones 7a to 7u and yields corresponding to the following products 8a to 8u, respectively. However, it was confirmed that the products 8a, 8b, 8c, 8e, 8f, 8g, 8h, 8j, 8l, 8m, n, s, and t are known compounds and are identical to the following reported data.
Kobayashi, S .; Ogawa, C .; Konishi, H .; Sugiura, MJ Am. Chem. Soc. 2003, 125, 6610.
Roush, WR; Adam, MA; Walts, AE; Harris, DJJ Am. Chem. Soc. 1986, 108, 3422.
Hirabayashi, R .; Ogawa, C .; Sugiura, M .; Kobayashi, SJ Am. Chem. Soc. 2001, 123, 9493.
Tan, KL; Jacobsen, EN Angew. Chem. Int. Ed. 2007, 46, 1315.

表６において、１価のヨウ化インジウム5 mol%存在下、一級、二級、三級の脂肪族アルデヒド由来のアシルヒドラゾンではいずれも反応が進行し、高い収率でホモアリルヒドラジド8を与えた(entry 1-8)。不飽和アルデヒド由来のアシルヒドラゾンでは、1,2付加体が高い収率で生成した(entry 9-11)。様々な芳香環・ヘテロ環を有するアシルヒドラゾンを用いても高い収率で反応が進行した(entry 12-18)。さらに、アルデヒド由来のみならずケトン由来のアシルヒドラゾンを用いても高い収率で反応が進行した(entry 19-21)。従って、N-アシルヒドラゾンの種々の官能基（ジメチルアミノ基、メトキシ基、クロロ基、エステル基、シロキシ基、ピリジル基、二重結合、三重結合など）が表６の反応条件によって影響を受けず、共存可能であることがわかる。 In Table 6, in the presence of 5 mol% of monovalent indium iodide, the reaction proceeded with acylhydrazones derived from primary, secondary, and tertiary aliphatic aldehydes to give homoallyl hydrazide 8 in high yield. (entry 1-8). In the acyl hydrazone derived from unsaturated aldehyde, 1,2-adduct was produced in high yield (entry 9-11). The reaction proceeded in high yield even with acylhydrazones having various aromatic rings and heterocycles (entry 12-18). Furthermore, the reaction proceeded in a high yield using not only aldehyde-derived but also ketone-derived acyl hydrazone (entry 19-21). Therefore, various functional groups (dimethylamino group, methoxy group, chloro group, ester group, siloxy group, pyridyl group, double bond, triple bond, etc.) of N-acylhydrazone are not affected by the reaction conditions in Table 6. It can be seen that they can coexist.

生成物8d； N'-(1-(1'-tert-butyldimethylsiloxy)hex-5-en-3-yl)benzohydrazide (; 表６のentry 4): ヒドラゾン8d から合成した黄色液体 (収率 96%)として得られ、式XXXII

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 0.05 (s, 6H), 0.86 (s, 9H), 1.66-1.72 (m, 2H), 2.24 (t, J = 6.8 Hz, 2H), 3.08-3.14 (m, 1H), 3.72-3.84 (m, 2H), 5.08-5.15 (m, 2H), 5.22 (br s, 1H), 5.80-5.91 (m, 1H), 7.37-7.48 (m, 3H), 7.71-7.73 (m, 2H), 8.19 (br s, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ= -5.39, -5.35, 18.25, 25.89, 35.93, 38.04, 58.14, 60.99, 117.50, 126.79, 128.52, 131.56, 133.03, 135.20, 166.58; IR (neat): ν = 3286, 3071, 2954, 2928, 2884, 2857, 1638, 1578, 1540, 1462, 1360, 1313, 1257, 1095, 1027, 914, 837, 805, 777, 696, 664, 514 cm^-1; HRMS (ESI) calcd. for C₁₉H₃₃N₂O₂Si⁺ = [M+H]⁺: m/z = 349.2306, found: m/z = 349.2294. Product 8d; N '-(1- (1'-tert-butyldimethylsiloxy) hex-5-en-3-yl) benzohydrazide (; entry 4 in Table 6): yellow liquid synthesized from hydrazone 8d (yield 96% ) And the formula XXXII

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 0.05 (s, 6H), 0.86 (s, 9H), 1.66-1.72 (m, 2H), 2.24 (t, J = 6.8 Hz, 2H), 3.08- 3.14 (m, 1H), 3.72-3.84 (m, 2H), 5.08-5.15 (m, 2H), 5.22 (br s, 1H), 5.80-5.91 (m, 1H), 7.37-7.48 (m, 3H) , 7.71-7.73 (m, 2H), 8.19 (br s, 1H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = -5.39, -5.35, 18.25, 25.89, 35.93, 38.04, 58.14, 60.99, 117.50 , 126.79, 128.52, 131.56, 133.03, 135.20, 166.58; IR (neat): ν = 3286, 3071, 2954, 2928, 2884, 2857, 1638, 1578, 1540, 1462, 1360, 1313, 1257, 1095, 1027, 914, 837, 805, 777, 696, 664, 514 cm ^-1 ; HRMS (ESI) calcd.for C ₁₉ H ₃₃ N ₂ O ₂ Si ⁺ = [M + H] ⁺ : m / z = 349.2306, found: m / z = 349.2294.

生成物8i；N'-(hexa-1,5-dien-3-yl)benzohydrazide (表６のentry 9): ヒドラゾン8i から合成した淡黄色固体 (収率 82%)として得られ、式XXXIII

で表されるものであった。
mp = 65.4-67.5 ℃; ¹H NMR (CDCl₃, 400 MHz): δ= 2.30 (dd, J = 6.8 Hz, J = 7.2 Hz, 2H), 3.54 (dt, J = 6.8 Hz, J = 7.2 Hz, 1H), 5.00 (br s, 1H), 5.10-5.23 (m, 4H), 5.66-5.77 (m, 1H), 5.78-5.90 (m, 1H), 7.38-7.52 (m, 3H), 7.61 (br s, 1H), 7.67-7.72 (m, 2H); ¹³C NMR (CDCl₃, 100 MHz): δ= 38.06, 62.96, 117.87, 118.10, 126.78, 128.69, 131.81, 132.89, 134.24, 138.52, 167.03; IR (neat): ν = 3281, 3076, 2980, 2908, 1641, 1604, 1578, 1537, 1460, 1324, 1067, 1027, 992, 921, 797, 694 cm^-1; HRMS (ESI) calcd. for C₁₃H₁₇N₂O⁺ = [M+H]⁺: m/z = 217.1335 and for C₁₃H₁₆N₂Na⁺ = [M+Na]⁺: m/z = 239.1155, found: m/z = 217.1339 (major) and 239.1160 (minor). Product 8i; N ′-(hexa-1,5-dien-3-yl) benzohydrazide (entry 9 in Table 6): obtained as a pale yellow solid (yield 82%) synthesized from hydrazone 8i and having the formula XXXIII

It was represented by.
mp = 65.4-67.5 ° C; ¹ H NMR (CDCl ₃ , 400 MHz): δ = 2.30 (dd, J = 6.8 Hz, J = 7.2 Hz, 2H), 3.54 (dt, J = 6.8 Hz, J = 7.2 Hz , 1H), 5.00 (br s, 1H), 5.10-5.23 (m, 4H), 5.66-5.77 (m, 1H), 5.78-5.90 (m, 1H), 7.38-7.52 (m, 3H), 7.61 ( br s, 1H), 7.67-7.72 (m, 2H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 38.06, 62.96, 117.87, 118.10, 126.78, 128.69, 131.81, 132.89, 134.24, 138.52, 167.03; IR (neat): ν = 3281, 3076, 2980, 2908, 1641, 1604, 1578, 1537, 1460, 1324, 1067, 1027, 992, 921, 797, 694 cm ^-1 ; HRMS (ESI) calcd. For C ₁₃ H ₁₇ N ₂ O ⁺ = [M + H] ⁺ : m / z = 217.1335 and for C ₁₃ H ₁₆ N ₂ Na ⁺ = [M + Na] ⁺ : m / z = 239.1155, found: m / z = 217.1339 (major) and 239.1160 (minor).

生成物8o；N'-(1-(2-methoxyphenyl)but-3-enyl)benzohydrazide (表６のentry 15): ヒドラゾン8o から合成した淡黄色液体 (収率 98%)として得られ、式XXXIV

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 2.40-2.50 (m, 1H), 2.51-2.60 (m, 1H), 3.76 (s, 3H), 4.60 (dd, J = 7.6 Hz, J = 8.0 Hz, 1H), 5.08-5.19 (m, 2H), 5.33 (br s, 1H), 5.83-5.95 (m, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.97 (dd, J = 7.2 Hz, J = 7.6 Hz, 1H), 7.21-7.52 (m, 6H), 7.58 (dd, J = 1.2 Hz, J = 7.2 Hz, 2H); ¹³C NMR (CDCl₃, 100 MHz): δ= 38.76, 55.34, 57.35, 110.66, 117.55, 120.62, 126.77, 127.43, 128.28, 128.55, 129.59, 131.60, 133.04, 135.14, 157.55, 166.79; IR (neat): ν = 3286, 3071, 2936, 2836, 1642, 1602, 1579, 1536, 1492, 1463, 1289, 1243, 1051, 1028, 917, 756, 694 cm^-1; HRMS (ESI) calcd. for C₁₈H₂₁N₂O₂ ⁺ = [M+H]⁺: m/z = 297.1598 and for C₁₈H₂₀N₂NaO₂ ⁺ = [M+Na]⁺: m/z = 319.1417, found: m/z = 297.1591 (major) and 319.1407 (minor). Product 8o; N ′-(1- (2-methoxyphenyl) but-3-enyl) benzohydrazide (entry 15 in Table 6): obtained as a pale yellow liquid (yield 98%) synthesized from hydrazone 8o and having the formula XXXIV

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 2.40-2.50 (m, 1H), 2.51-2.60 (m, 1H), 3.76 (s, 3H), 4.60 (dd, J = 7.6 Hz, J = 8.0 Hz, 1H), 5.08-5.19 (m, 2H), 5.33 (br s, 1H), 5.83-5.95 (m, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.97 (dd, J = 7.2 Hz, J = 7.6 Hz, 1H), 7.21-7.52 (m, 6H), 7.58 (dd, J = 1.2 Hz, J = 7.2 Hz, 2H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 38.76 , 55.34, 57.35, 110.66, 117.55, 120.62, 126.77, 127.43, 128.28, 128.55, 129.59, 131.60, 133.04, 135.14, 157.55, 166.79; IR (neat): ν = 3286, 3071, 2936, 2836, 1642, 1602, 1579, 1536, 1492, 1463, 1289, 1243, 1051, 1028, 917, 756, 694 cm ^-1 ; HRMS (ESI) calcd.for C ₁₈ H ₂₁ N ₂ O ₂ ⁺ = [M + H] ⁺ : m / z = 297.1598 and for C ₁₈ H ₂₀ N ₂ NaO ₂ ⁺ = [M + Na] ⁺ : m / z = 319.1417, found: m / z = 297.1591 (major) and 319.1407 (minor).

生成物8p；N'-(1-(4-(dimethylamino)phenyl)but-3-enyl)benzohydrazide (表６のentry 16): ヒドラゾン8p から合成した淡黄色液体 (収率 75%)として得られ、式XXXV

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 2.43-2.56 (m, 2H), 2.94 (s, 6H), 4.05 (t, J = 6.8 Hz, 1H), 5.08-5.26 (m, 3H), 5.77-5.90 (m, 1H), 6.71 (d, J = 8.4 Hz, 2H), 7.21-7.48 (m, 6H), 7.58 (dd, J = 1.6 Hz, J = 7.2 Hz, 2H); ¹³C NMR (CDCl₃, 100 MHz): δ= 40.01, 40.49, 40.49, 63.25, 112.42, 117.52, 126.77, 128.45, 128.45, 128.92, 131.53, 132.91, 134.89, 150.04, 166.88; IR (neat): ν = 3301, 3072, 2978, 2888, 2802, 1659, 1652, 1579, 1524, 1455, 1353, 1227, 1189, 1164, 1132, 1062, 1027, 994, 947, 913, 815, 731, 694, 647, 540 cm^-1; HRMS (ESI) calcd. for C₁₉H₂₄N₃O⁺ = [M+H]⁺: m/z = 310.1914 and for C₁₉H₂₃N₃NaO⁺ = [M+Na]⁺: m/z = 332.1733, found: m/z = 310.1907 (minor) and 332.1721 (major). Product 8p; N '-(1- (4- (dimethylamino) phenyl) but-3-enyl) benzohydrazide (entry 16 in Table 6): obtained as a pale yellow liquid (yield 75%) synthesized from hydrazone 8p , Formula XXXV

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 2.43-2.56 (m, 2H), 2.94 (s, 6H), 4.05 (t, J = 6.8 Hz, 1H), 5.08-5.26 (m, 3H), 5.77-5.90 (m, 1H), 6.71 (d, J = 8.4 Hz, 2H), 7.21-7.48 (m, 6H), 7.58 (dd, J = 1.6 Hz, J = 7.2 Hz, 2H); ¹³ C NMR (CDCl ₃ , 100 MHz): δ = 40.01, 40.49, 40.49, 63.25, 112.42, 117.52, 126.77, 128.45, 128.45, 128.92, 131.53, 132.91, 134.89, 150.04, 166.88; IR (neat): ν = 3301, 3072 , 2978, 2888, 2802, 1659, 1652, 1579, 1524, 1455, 1353, 1227, 1189, 1164, 1132, 1062, 1027, 994, 947, 913, 815, 731, 694, 647, 540 cm ^-1 ; HRMS (ESI) calcd.for C ₁₉ H ₂₄ N ₃ O ⁺ = [M + H] ⁺ : m / z = 310.1914 and for C ₁₉ H ₂₃ N ₃ NaO ⁺ = [M + Na] ⁺ : m / z = 332.1733, found: m / z = 310.1907 (minor) and 332.1721 (major).

生成物8r；N'-(1-(pyridin-3-yl)but-3-enyl)benzohydrazide (表６のentry 18): ヒドラゾン8r から合成した白色固体 (収率 86%)として得られ、式XXXVI

で表されるものであった。
mp = 118.4-121.6 ℃ ; ¹H NMR (CDCl₃, 400 MHz): δ= 2.42-2.59 (m, 2H), 4.22 (t, J = 6.8 Hz, 1H), 5.12-5.24 (m, 3H), 5.76-5.88 (m, 1H), 7.23-7.28 (m, 1H), 7.36 (dd, J = 7.2 Hz, J = 8.0 Hz, 2H), 7.46 (dd, J = 7.2 Hz, J = 8.0 Hz, 1H), 7.58-7.71 (m, 4H), 8.48 (dd, J = 4.4 Hz, J = 4.8 Hz, 1H), 8.59 (d, J = 2.4 Hz, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ= 40.23, 61.69, 118.78, 123.50, 126.84, 128.67, 131.96, 132.55, 133.63, 135.43, 137.26, 149.05, 149.61, 167.63; IR (KBr): ν = 3436, 3019, 1657, 1579, 1528, 1459, 1429, 1363, 1324, 1216, 1085, 1028, 928, 770, 669 cm^-1; HRMS (ESI) calcd. for C₁₆H₁₈N₃O⁺ = [M+H]⁺: m/z = 268.1444 and for C₁₆H₁₇N₃NaO⁺ = [M+Na]⁺: m/z = 290.1264, found: m/z = 268.1440 (major) and 290.1274 (minor). Product 8r; N '-(1- (pyridin-3-yl) but-3-enyl) benzohydrazide (entry 18 in Table 6): obtained as a white solid (86% yield) synthesized from hydrazone 8r XXXVI

It was represented by.
mp = 118.4-121.6 ° C; ¹ H NMR (CDCl ₃ , 400 MHz): δ = 2.42-2.59 (m, 2H), 4.22 (t, J = 6.8 Hz, 1H), 5.12-5.24 (m, 3H), 5.76-5.88 (m, 1H), 7.23-7.28 (m, 1H), 7.36 (dd, J = 7.2 Hz, J = 8.0 Hz, 2H), 7.46 (dd, J = 7.2 Hz, J = 8.0 Hz, 1H ), 7.58-7.71 (m, 4H), 8.48 (dd, J = 4.4 Hz, J = 4.8 Hz, 1H), 8.59 (d, J = 2.4 Hz, 1H); ¹³ C NMR (CDCl ₃ , 100 MHz) : δ = 40.23, 61.69, 118.78, 123.50, 126.84, 128.67, 131.96, 132.55, 133.63, 135.43, 137.26, 149.05, 149.61, 167.63; IR (KBr): ν = 3436, 3019, 1657, 1579, 1528, 1459, 1429, 1363, 1324, 1216, 1085, 1028, 928, 770, 669 cm ^-1 ; HRMS (ESI) calcd.for C ₁₆ H ₁₈ N ₃ O ⁺ = [M + H] ⁺ : m / z = 268.1444 and for C ₁₆ H ₁₇ N ₃ NaO ⁺ = [M + Na] ⁺ : m / z = 290.1264, found: m / z = 268.1440 (major) and 290.1274 (minor).

生成物8u；Methyl 2-(benzamido)-2-methylpent-4-enoate(表６のentry 21): ヒドラゾン8u から合成した淡黄色液体 (収率 89%)として得られ、式XXXVII

で表されるものであった。
¹H NMR (CDCl₃, 400 MHz): δ= 1.35 (s, 3H), 2.44-2.55 (m, 2H), 3.71 (s, 3H), 5.03 (br s, 1H), 5.10-5.14 (m, 2H), 5.73-5.83 (m, 1H), 7.36-7.48 (m, 3H), 7.70 (d, J = 6.8 Hz, 2H), 7.97 (br s, 1H); ¹³C NMR (CDCl₃, 100 MHz): δ= 21.04, 41.43, 52.26, 64.95, 119.46, 126.85, 128.57, 131.70, 132.10, 132.79, 166.76, 175.23; IR (neat): ν = 3278, 3077, 2943, 2891, 2865, 2170, 1643, 1604, 1579, 1532, 1463, 1384, 1365, 1316, 1071, 1027, 996, 918, 883, 793, 692, 677 cm^-1; HRMS (ESI) calcd. fo C₁₄H₁₉N₂O₃ ⁺ = [M+H]⁺: m/z = 263.1390, found: m/z = 263.1401. Product 8u; Methyl 2- (benzamido) -2-methylpent-4-enoate (entry 21 in Table 6): obtained as a pale yellow liquid (yield 89%) synthesized from hydrazone 8u, which has the formula XXXVII

It was represented by.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 1.35 (s, 3H), 2.44-2.55 (m, 2H), 3.71 (s, 3H), 5.03 (br s, 1H), 5.10-5.14 (m, 2H), 5.73-5.83 (m, 1H), 7.36-7.48 (m, 3H), 7.70 (d, J = 6.8 Hz, 2H), 7.97 (br s, 1H); ¹³ C NMR (CDCl ₃ , 100 MHz ): δ = 21.04, 41.43, 52.26, 64.95, 119.46, 126.85, 128.57, 131.70, 132.10, 132.79, 166.76, 175.23; IR (neat): ν = 3278, 3077, 2943, 2891, 2865, 2170, 1643, 1604 , 1579, 1532, 1463, 1384, 1365, 1316, 1071, 1027, 996, 918, 883, 793, 692, 677 cm ^-1 ; HRMS (ESI) calcd.fo C ₁₄ H ₁₉ N ₂ O ₃ ⁺ = [ M + H] ⁺ : m / z = 263.1390, found: m / z = 263.1401.

<溶媒による効果>
式XXXVIII

で表される反応により、ケトンのアリル化を行った。溶媒であるトルエンに対し、添加剤としてメタノールを加えた場合（収率95％）、溶媒としてテトラヒドロフラン（THF）を用いた場合（収率11％）と比較して高い収率が得られた。これより、添加剤としてメタノールを加えたトルエンを溶媒として用いると、ケトンのアリル化にも有効であると考えられる。 <Effects by solvent>
Formula XXXVIII

Allylation of the ketone was carried out by the reaction represented by: A higher yield was obtained compared to the case where methanol was added as an additive (yield 95%) and the case where tetrahydrofuran (THF) was used as a solvent (yield 11%) with respect to toluene as a solvent. From this, it is considered that when toluene added with methanol as an additive is used as a solvent, it is also effective for allylation of ketones.

以上のように、本発明によれば、ケトン又はN-アシルヒドラゾンのアリル化反応において、温和な条件かつ簡便な方法で反応が進行し、インジウム（０価又は１価）は触媒量で十分である（従来は量論量以上必要）。又、本発明によれば、広い基質一般性を有し、種々の官能基が共存可能であるため、天然物合成等の多段階合成に適用可能である。さらに、生成物であるホモアリルアルコール又はホモアリルヒドラジドは有用な中間体となる。 As described above, according to the present invention, in the allylation reaction of a ketone or N-acyl hydrazone, the reaction proceeds under a mild condition and with a simple method, and a catalytic amount of indium (zero or monovalent) is sufficient. Yes (conventionally more than stoichiometric). In addition, according to the present invention, since it has wide substrate generality and various functional groups can coexist, it can be applied to multi-step synthesis such as natural product synthesis. In addition, the product homoallylic alcohol or homoallyl hydrazide is a useful intermediate.

Claims

Formula I

A ketone or N-acylhydrazone is allylated with a boron-containing allylating agent consisting of pinacolylallylborate represented by the formula: 1-50 mol% of monovalent or zero-valent indium with respect to the ketone or N-acylhydrazone. A method for producing homoallyl alcohol or homoallyl hydrazide used as a catalyst,
The ketone is represented by R ₁ —C═O—R ₂ (R ₁ and R ₂ are an aromatic group, a heterocyclic group, and an aliphatic group),
Said N-acylhydrazone has the formula XXIX

(Wherein R ⁴ is an aromatic group, aliphatic group or heterocyclic group; R ⁵ is a hydrogen atom or an aliphatic group; R ⁶ is an aromatic group), and a method for producing homoallylic alcohol or homoallyl hydrazide .