JPS6225675B2 - - Google Patents
Info
- Publication number
- JPS6225675B2 JPS6225675B2 JP17680083A JP17680083A JPS6225675B2 JP S6225675 B2 JPS6225675 B2 JP S6225675B2 JP 17680083 A JP17680083 A JP 17680083A JP 17680083 A JP17680083 A JP 17680083A JP S6225675 B2 JPS6225675 B2 JP S6225675B2
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- asymmetric
- compounds
- present
- group
- 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
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- -1 allyltin compound Chemical class 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000006717 asymmetric allylation reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 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
- 150000004820 halides Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UQDKSKMEPAASFW-UHFFFAOYSA-N 1-chlorobutan-2-ylbenzene Chemical compound CCC(CCl)C1=CC=CC=C1 UQDKSKMEPAASFW-UHFFFAOYSA-N 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- MJHZPMRMLWHVDR-UHFFFAOYSA-M [Cl-].C1(=CC=CC=C1)C(C[Mg+])CC Chemical compound [Cl-].C1(=CC=CC=C1)C(C[Mg+])CC MJHZPMRMLWHVDR-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006293 aldehyde allylation reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- YLKVXRKJVMGRRR-UHFFFAOYSA-L dibromo-bis(prop-2-enyl)stannane Chemical compound C=CC[Sn](Br)(Br)CC=C YLKVXRKJVMGRRR-UHFFFAOYSA-L 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- GMDGXJQUWIQOLE-UHFFFAOYSA-N prop-2-enylborane Chemical class BCC=C GMDGXJQUWIQOLE-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 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 the above silicon compounds are 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、
光学活性２―フエニルブチルハライドから常法に
よつてグリニヤール試薬を製造し、これとジアリ
ル錫ハライドとを適当な溶媒中で反応させること
によつて得られる。 The optically active organotin compound of formula () of the present invention is:
It can be obtained by preparing a Grignard reagent from optically active 2-phenylbutyl halide by a conventional method and reacting this with diallyltin halide in an appropriate solvent.
上記２―フエニルブチルハライドおよびジアリ
ル錫ハライドにおけるハロゲンとしては、塩素，
臭素，ヨウ素が挙げられる。また反応溶媒として
は、テトラヒドロフラン，ジエチルエーテル，ジ
メトキシエタン等が挙げられ、反応温度は、通常
―100〜120℃が適当である。 The halogens in the above 2-phenylbutyl halide and diallyltin halide include chlorine,
Examples include bromine and iodine. Examples of the reaction solvent include tetrahydrofuran, diethyl ether, dimethoxyethane, etc., and the reaction temperature is usually -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、こ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 homoallylic 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
（＋）―１―クロロ―２―フエニルブタン（光
学純度97％）18.0ｇ（107ｍ mol）より調製した
２―フエニルブチルマグネシウムクロライドのテ
トラヒドロフラン溶液20mlに、ジアリル錫ジブロ
マイド12.8ｇ（36ｍ mol）を加え、室温で１時
間攪拌した後、30分間還流させた。反応混合物に
ヘキサン100mlを加えて濾過した後、濾液を濃縮
し、得られた油分を蒸留して目的物（―）―ジア
リルビス（２―フエニルブチル）錫15.1ｇを得た
（収率90％）。Example 12.8 g (36 m mol) of diallyltin dibromide was added to 20 ml of a tetrahydrofuran solution of 2-phenylbutylmagnesium chloride prepared from 18.0 g (107 m mol) of (+)-1-chloro-2-phenylbutane (optical purity 97%). ) was added, stirred at room temperature for 1 hour, and then refluxed for 30 minutes. After adding 100 ml of hexane to the reaction mixture and filtering it, the filtrate was concentrated, and the resulting oil was distilled to obtain 15.1 g of the target product (-)-diallylbis(2-phenylbutyl)tin (yield 90%).
得られた目的物の物性値は以下の通りである。 The physical properties of the obtained target product are as follows.
沸点 210℃／0.15mmＨｇ
〔α〕２３ Ｄ―38.1゜，（Ｃ 0.97，ベンゼン）
元素分析
実測値 C67.17％ Ｈ 7.94％
理論値 C66.83％ Ｈ 7.77％
NMR（CCl4溶媒 TMS規準δ）
0.69（6H），0.87〜1.93（12H），2.02〜2.85
（2H），4.40〜4.88（4H），5.16〜6.03（2H），
7.00〜7.30（10H） Boiling point 210℃/0.15mmHg [α] 23 D -38.1゜, (C 0.97, benzene) Elemental analysis Actual value C67.17% H 7.94% Theoretical value C66.83% H 7.77% NMR (CCl 4 solvent TMS standard δ) 0.69 (6H), 0.87~1.93 (12H), 2.02~2.85
(2H), 4.40-4.88 (4H), 5.16-6.03 (2H),
7.00~7.30 (10H)
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 |
|---|---|---|---|
| JP17680083A JPS6067486A (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 |
|---|---|---|---|
| JP17680083A JPS6067486A (en) | 1983-09-24 | 1983-09-24 | Optically active organotin compound containing asymmetric group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6067486A JPS6067486A (en) | 1985-04-17 |
| JPS6225675B2 true JPS6225675B2 (en) | 1987-06-04 |
Family
ID=16020059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17680083A Granted JPS6067486A (en) | 1983-09-24 | 1983-09-24 | Optically active organotin compound containing asymmetric group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6067486A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2071092A1 (en) * | 1991-06-14 | 1992-12-15 | Roger M. Freidinger | 1,4-benzodiazepines with 5-membered heterocyclic rings |
-
1983
- 1983-09-24 JP JP17680083A patent/JPS6067486A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6067486A (en) | 1985-04-17 |
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