JPS6225676B2 - - Google Patents
Info
- Publication number
- JPS6225676B2 JPS6225676B2 JP17680183A JP17680183A JPS6225676B2 JP S6225676 B2 JPS6225676 B2 JP S6225676B2 JP 17680183 A JP17680183 A JP 17680183A JP 17680183 A JP17680183 A JP 17680183A JP S6225676 B2 JPS6225676 B2 JP S6225676B2
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- asymmetric
- reaction
- allyl
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- -1 allyltin compound Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 238000006717 asymmetric allylation reaction Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- ODOPKAJVFRHHGM-UHFFFAOYSA-N phenyltin Chemical compound [Sn]C1=CC=CC=C1 ODOPKAJVFRHHGM-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006293 aldehyde allylation reaction Methods 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- DQEUYIQDSMINEY-UHFFFAOYSA-M magnesium;prop-1-ene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C=C DQEUYIQDSMINEY-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- GMDGXJQUWIQOLE-UHFFFAOYSA-N prop-2-enylborane Chemical class BCC=C GMDGXJQUWIQOLE-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、不斉基を有する光学的に活性な有機
錫化合物に関する。更に詳細には、本発明は、下
記式（）で表わされる不斉基を有し、不斉合成
反応に有用な光学活性有機錫化合物に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to optically active organotin compounds having an asymmetric group. More specifically, the present invention relates to an optically active organotin compound having an asymmetric group represented by the following formula () and useful for asymmetric synthesis reactions.
有機錫化合物の中には、官能基の転換試剤や触
媒として有用なものが多いが、不斉合成の如く更
に精密な選択性が要求される場合には、従来公知
の有機錫化合物では全く効果がなかつた。 Many organotin compounds are useful as functional group conversion agents and catalysts, but in cases where more precise selectivity is required, such as in asymmetric synthesis, conventionally known organotin compounds are completely ineffective. I was bored.
本発明は、反応性官能基としてアリル基を有す
るアリル錫化合物に光学活性な不斉基を導入した
光学活性な新規有機錫化合物に関するものであ
り、このものは次式（）で示されるように、ケ
トンまたはアルデヒドの不斉アリル化反応試剤と
して有用であることが見出された。 The present invention relates to a new optically active organotin compound in which an optically active asymmetric group is introduced into an allyltin compound having an allyl group as a reactive functional group, and this compound is as shown by the following formula (). , was found to be useful as a reagent for asymmetric allylation of ketones or aldehydes.
但し、上記式（）中、R1，R2は水素原子ま
たは有機基であり、R1とR2が同一であることは
ない。 However, in the above formula (), R 1 and R 2 are hydrogen atoms or organic groups, and R 1 and R 2 are not the same.
上記式（）によつて得られるホモアリルアル
コール類は合成中間体として有用なものが多い。
従来においては、光学活性アリルケイ素化合物や
光学活性アリルホウ素化合物による不斉アリル化
反応が若干例報告されているが、上記ケイ素化合
物ではアリル基がフエニル置換された特別な場合
に限られること、又上記ホウ素化合物では、この
ものが大気中で不安定なため取扱上の制限がある
こと、また該化合物の再使用が困難であることな
どの欠点があつた。 Many of the homoallyl alcohols obtained by the above formula () are useful as synthetic intermediates.
In the past, some examples of asymmetric allylation reactions using optically active allyl silicon compounds and optically active allyl boron compounds have been reported, but in the above silicon compounds, it is limited to special cases where the allyl group is substituted with phenyl. The above-mentioned boron compounds have drawbacks such as being unstable in the atmosphere, which imposes restrictions on handling, and that it is difficult to reuse the compounds.
本発明の式（）の化合物は、利用価値の高い
全水素置換アリル基の場合でも適用でき、一般性
が高いだけでなく、空気中でも安定で、しかも光
学活性有機基が再使用可能な形で回収できるなど
不斉アリル化反応試剤として極めて有用性が高
い。 The compound of formula () of the present invention can be applied even in the case of a fully hydrogen-substituted allyl group, which has high utility value, and is not only highly general, but also stable in the air, and the optically active organic group is in a reusable form. It is extremely useful as an asymmetric allylation reaction reagent because it can be recovered.
本発明の式（）の光学活性有機錫化合物は、
次のような方法で製造することができる。 The optically active organotin compound of formula () of the present invention is:
It can be manufactured by the following method.
公知の方法（J.S.Filippo，JrらJ.Am.Chem.
Soc.104，2831（1982）で得られる、光学活性
（２―オクチル）トリフエニル錫を臭素と反応さ
せて光学活性（２―オクチル）フエニル錫ジブロ
マイドとし、これをアリルマグネシウムハライド
またはトシラートと反応させると得られる。 Known methods (JS Filippo, Jr. et al. J. Am. Chem.
Soc. 104 , 2831 (1982) by reacting optically active (2-octyl) triphenyltin with bromine to give optically active (2-octyl)phenyltin dibromide, which is then reacted with allylmagnesium halide or tosylate. is obtained.
上記製法において、臭素との反応は、四塩素炭
素，クロロホルム，エーテル等の溶媒中で行なう
ことができる。反応温度は通常−100〜120℃の範
囲である。また、アリルグリニヤール試薬との反
応は、エーテル，テトラヒドロフラン，ジメトキ
シエタン等の溶媒中でなうことができ、反応温度
は通常−100〜120℃の範囲である。 In the above production method, the reaction with bromine can be carried out in a solvent such as tetrachloride, chloroform, or ether. The reaction temperature is usually in the range of -100 to 120°C. Further, the reaction with the allyl Grignard reagent can be carried out in a solvent such as ether, tetrahydrofuran, dimethoxyethane, etc., and the reaction temperature is usually in the range of -100 to 120°C.
本発明の光学活性有機錫化合物は、前記したよ
うに、アルデヒドまたはケトンと前記式（）の
ように不斉反応させ、それを加水分解することに
より光学活性なホモアリルアルコールを得ること
ができる。例えばアルデヒドとしてｎ―
C3H7CHO、ｔ―C4H9CHO、ｎ―C8H17CHO、
C6H5CH＝CHCHO、C6H5CHO等を用いて対応す
る光学活性ホモアリルアルコールを得ることがで
きる。 As described above, the optically active organotin compound of the present invention can be subjected to an asymmetric reaction with an aldehyde or ketone as shown in the above formula (), and then hydrolyzed to obtain optically active homoallyl alcohol. For example, as an aldehyde, n-
C 3 H 7 CHO, t-C 4 H 9 CHO, n-C 8 H 17 CHO,
The corresponding optically active homoallyl alcohol can be obtained using C 6 H 5 CH=CHCHO, C 6 H 5 CHO, etc.
更に、反応後適当な処理を行なうことにより、
光学活性な置換基は繰返し使用可能な形で回収さ
れる。 Furthermore, by performing appropriate treatment after the reaction,
The optically active substituent is recovered in a form that can be used repeatedly.
以下実施例によつて本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例
（−）―（Ｒ）―２―オクチルトリフエニル錫
9.26ｇ（20m mol）の四塩化炭素溶液100mlに、
臭素3.36ｇ（42m mol）を０℃で滴下し、室温で
30分間反応後減圧下で溶媒を留去して（−）―２
―オクチルフエニル錫ジブロマイド9.1ｇを得た
（収率97％、〔α〕２３ Ｄ―20.1゜，（C4.00，ベンゼ
ン））。Example (-)-(R)-2-octyltriphenyltin
9.26 g (20 mmol) in 100 ml of carbon tetrachloride solution,
3.36 g (42 mmol) of bromine was added dropwise at 0°C, and the mixture was heated to room temperature.
After reacting for 30 minutes, the solvent was distilled off under reduced pressure to give (-)-2
-9.1 g of octylphenyltin dibromide was obtained (yield 97%, [α] 23 D -20.1°, (C4.00, benzene)).
上記（−）―２―オクチルフエニル錫ジブロマ
イド9.0ｇ（19m mol）のテトラヒドロフラン溶
液40mlを、アリルブロマイド9.2ｇ（76m mol）
から調製したアリルマグネシウムブロマイドのテ
トラヒドロフラン溶液60mlに−10℃で滴下し、１
時間還流後反応液にヘキサン100mlを加えて濾過
し、濾液の溶媒を留去し、残留物を減圧蒸留する
と、目的物（−）―ジアリル（２―オクチル）フ
エニル錫6.3ｇが得られた（収率85％）。得られた
目的物の沸点175〜180℃／0.2mmHg、〔α〕２３ Ｄ―
21.2゜（C3.52，ベンゼン）であつた。目的物の
核磁気共鳴スペクトル（CCl4溶媒、TMS規準）
と赤外線吸収スペクトル（薄膜法）を第１図及び
第２図に示した。 Add 40 ml of a tetrahydrofuran solution of 9.0 g (19 mmol) of the above (-)-2-octylphenyltin dibromide to 9.2 g (76 mmol) of allyl bromide.
Add dropwise at -10°C to 60ml of a tetrahydrofuran solution of allylmagnesium bromide prepared from
After refluxing for a period of time, 100 ml of hexane was added to the reaction solution and filtered, the solvent of the filtrate was distilled off, and the residue was distilled under reduced pressure to obtain 6.3 g of the target product (-)-diallyl(2-octyl)phenyltin ( yield 85%). Boiling point of the obtained target product: 175-180℃/0.2mmHg, [α] 23D -
It was 21.2° (C3.52, benzene). Nuclear magnetic resonance spectrum of target product (CCl 4 solvent, TMS standard)
and infrared absorption spectra (thin film method) are shown in Figures 1 and 2.
第１図は実施例によつて得られた（−）―ジア
リル（２―オクチル）フエニル錫の核磁気共鳴ス
ペクトルを示し、第２図は同物質の赤外線吸収ス
ペクトルを示す。
FIG. 1 shows the nuclear magnetic resonance spectrum of (-)-diallyl(2-octyl)phenyltin obtained in the example, and FIG. 2 shows the infrared absorption spectrum of the same substance.
Claims (1)
学活性有機錫化合物。 [Scope of Claims] 1. An optically active organotin compound having an asymmetric group represented by the following formula ().
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17680183A JPS6067487A (en) | 1983-09-24 | 1983-09-24 | Optically active organotin compound containing asymmetric group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17680183A JPS6067487A (en) | 1983-09-24 | 1983-09-24 | Optically active organotin compound containing asymmetric group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6067487A JPS6067487A (en) | 1985-04-17 |
| JPS6225676B2 true JPS6225676B2 (en) | 1987-06-04 |
Family
ID=16020077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17680183A Granted JPS6067487A (en) | 1983-09-24 | 1983-09-24 | Optically active organotin compound containing asymmetric group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6067487A (en) |
-
1983
- 1983-09-24 JP JP17680183A patent/JPS6067487A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6067487A (en) | 1985-04-17 |
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