JPS6067486A - Optically active organotin compound containing asymmetric group - Google Patents
Optically active organotin compound containing asymmetric groupInfo
- Publication number
- JPS6067486A JPS6067486A JP17680083A JP17680083A JPS6067486A JP S6067486 A JPS6067486 A JP S6067486A JP 17680083 A JP17680083 A JP 17680083A JP 17680083 A JP17680083 A JP 17680083A JP S6067486 A JPS6067486 A JP S6067486A
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- organotin compound
- compound containing
- group
- asymmetric 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- -1 2-phenylbutyl halide Chemical class 0.000 abstract description 5
- 238000006717 asymmetric allylation reaction Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 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 abstract description 3
- 150000004820 halides Chemical class 0.000 abstract description 3
- 150000002576 ketones Chemical class 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- UQDKSKMEPAASFW-UHFFFAOYSA-N 1-chlorobutan-2-ylbenzene Chemical compound CCC(CCl)C1=CC=CC=C1 UQDKSKMEPAASFW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006293 aldehyde allylation reaction Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 abstract 1
- 239000007818 Grignard reagent Substances 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 150000004795 grignard reagents Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 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
- 150000001298 alcohols Chemical class 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
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
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（Ｉ）で表
わされる不斉基を右ザる光学活性有機錫化合物を提供す
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 provides an optically active organotin compound having an asymmetric group represented by the following formula (I).
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仝
く効宋がなかった。Many organotin compounds are useful as functional group conversion reagents and catalysts, but in cases where more precise selectivity is required, such as in asymmetric synthesis, conventionally known organotin compounds cannot be used. There was no Song Dynasty.
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
有機錫化合物をｌｊ）供するものであり、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ｌ〔。The present invention provides a novel optically active organotin compound lj) 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 has the following formula (][) As shown in [1], it was found to be useful as a reagent for asymmetric allylation of ketones or aldehydes.
但し、上記式（Ｉ）中、Ｒ’、Ｒ２は水素原子または有
機具であり、Ｒ１どＲ２が同一であることはない。However, in the above formula (I), R' and R2 are hydrogen atoms or organic moieties, and R1 and R2 are not the same.
上記式（Ｉｎ）によっ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Ｊ３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Ｊ：る不斉アリル化反応が若干側報告され
ているが、上記ケイ素化合物ではアリル基がフェニル置
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
どの欠点があった。Many of the homoallyl alcohols obtained by the above formula (In) are useful as synthetic intermediates. Conventionally, some asymmetric allylation reactions have been reported in optically active allyl silicon compounds and optically active allyl boron compounds, but in the special case where the allyl group is phenyl-substituted in the above silicon compounds, Furthermore, the boron compounds mentioned above 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（Ｉ）の化合物は、利用４＋ｎ白１（ｊの高
い全水素置換アリル基の場合でも適用でき、−膜性が高
いだけでなく−、空気中でも安定−（゛、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（小めて有用性が高い。The compound of formula (I) of the present invention can be applied even in the case of a fully hydrogen-substituted allyl group with a high utilization 4 + n white 1 (j), and has not only high film properties but also stability in air (゛, and optical activity. It is highly useful as an asymmetric allylation reaction reagent (although small in size), as the organic group can be recovered in a reusable form.
本発明の式（Ｉ）の光学活性有機錫化合物は、光学活性
２−フェニルブチルハライドから常法によってグリニヤ
ール試桑を製造し、これとジアリル錫ハライドとを適当
な溶媒中で反応さぼることによって得られる。The optically active organotin compound of formula (I) of the present invention can be obtained by preparing a Grignard sample from optically active 2-phenylbutyl halide by a conventional method, and stopping the reaction between this and diallyltin halide in an appropriate solvent. It will be done.
上記２−フェ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“Ｃ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１〜ラヒドロ
スラン、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 ’Ｃが適当
Ｃある。The halogen "C" in the above-mentioned 2-phenylbutyl halide and diallyltin halide includes chlorine, bromine, and iodine. Examples of the reaction solvent include Te1-lahydrosurane, diethyl ether, dimethoxyethane, etc., and the reaction temperature is , usually -100 to 120'C is suitable.
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（ＩＩ）のＪ：うに不斉
反応さけ、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ｕｃ３１−１２（１）Ｏ，ｔ −Ｃ４Ｈｔ（
１）Ｏ、ＴＬ −Ｃｇ Ｈｔ７ ＣＨＯ，Ｃｂ ｌ−１
ｓ Ｇ（＝ ＣＨＧ（○ 、ＣａＨｓ０４０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 undergoes an asymmetric reaction with an aldehyde or a ketone in formula (II), and can be hydrolyzed to obtain an optically active homoallylic alcohol. can. For example, as an aldehyde, uc31-12(1)O,t -C4Ht(
1) O, TL -Cg Ht7 CHO, Cb l-1
sG(=CHG(○), the corresponding optically active homoallylic alcohol can be obtained using CaHs040, 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 can be recovered in a form that can be used repeatedly.
以下実施例によって本発明を説明する。The present invention will be explained below with reference to Examples.
実施例
（＋）−ｉ−クロロ−２−フェニルブタン（光学純度９
７％） １８．０ｇ （１０７ｍ ｍｏｌ）より調製し
た２−フェ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１１２０ｍ１に、ジアリル錫ジブロマイ
ド１２．８（＋ （３Ｃｉｍ ｍｏｌ）を加え、室温で
１時間撹拌した後、３０分間還流させた。反応混合物
にヘキリーン１００ ｍｌを加えて濾過した後、濾液を
ｍ縮し、得られた油分を蒸留して目的物（−）−ジアリ
ルどス（２−フェニルブチル）錫１５．１ｇを得たく収
率９０％）。Example (+)-i-chloro-2-phenylbutane (optical purity 9
To 1,120 ml of a solution of 2-phenylbutylmagnesium chloride in tetrahydrofuran prepared from 18.0 g (107 mmol) of 2-phenylbutylmagnesium chloride, 12.8 (3 cm mol) of diallytin dibromide was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was refluxed for 100 ml and filtered.The filtrate was condensed and the resulting oil was distilled to obtain the desired product (-)-diallyldos(2-phenylbutyl)tin15. 1 g (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°Ｇ ／ ０．１５ ｕｎ ｆｉｇ（α１
ｏ−３８，１°、（Ｃ０８９７、ヘンセ＞）元素分析
実測値 Ｃ６７，１７％ ｌ−１７，９／１％理論値
０６６．８３％ ｌ−１７，７７％ＮＭＲ＜Ｃ印４溶媒
Ｔ Ｍ Ｓ ＸＩ準δ）０．６９ （６ｌ−（）、０
．８７〜１．９３ （１２＋−１） 。Boiling point 210°G / 0.15 un fig (α1
o-38,1°, (C0897, Hense>) Elemental analysis actual value C67,17% l-17,9/1% theoretical value
066.83% l-17,77%NMR<C mark 4 solvent T M S XI quasi δ) 0.69 (6l-(), 0
．． 87-1.93 (12+-1).
２．０２〜２．８５ （２Ｎ ＞’、４．４０〜４．８
８（４Ｈ）、５．１６〜６．０３ （２１−１） 。2.02~2.85 (2N>', 4.40~4.8
8(4H), 5.16-6.03 (21-1).
７．００〜７．３０ （１０１−１＞
出願人 大阪曹達株式会ネ」
代理人 弁理士 間予 透
手続補正書く自発）
昭和５９年 ６月１９日
１、事件の表示 昭和５８年特許願第１７６８００号２
、発明の名称 不斉基を有する光学活性有機錫化合物３
、ン市正をする者
事件との関係 特許出願人
４、代理人
〒５５０ 大阪市西区江戸堀１丁目１０番８号６、補正
の内容
（１）明細書第１真下第３行〜下第１行［不斉基を有す
る・・・提供するもの−である。」を］不ハ基を有し、
不斉合成反応に有用な光学活１（１有機錫化合物に関す
るものである。ｊと８）正づる。7.00 - 7.30 (101-1> Applicant: Osaka Soda Co., Ltd. Agent: Patent Attorney, Intermediate, volunteer to write amendments to transparent procedures) June 19, 1980 1, Indication of case: 1988 Patent Application No. 176800 No. 2
, Title of the invention Optically active organotin compound having an asymmetric group 3
, Relationship with the case of a person acting as a city attorney Patent applicant 4, Agent 1-10-8-6, Edobori, Nishi-ku, Osaka 550 Contents of amendment (1) Specification 1, line 3 to bottom 1 Line [having an asymmetric group...is provided. ”] has a hydrogen group,
Correct the optical activity 1 (1 concerning organotin compounds. j and 8) useful in asymmetric synthesis reactions.
（２）同書第２真下第５行〜下第４行［を提供りる」を
１に関する」と訂正する。(2) Correct "provide" to "relating to 1" in lines 5 to 4, directly below the second part of the same book.
Claims (1)
錫化合物。 （１）[Scope of Claims] An optically active organotin compound having an asymmetric group represented by the following formula (I>). (1)
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 true JPS6067486A (en) | 1985-04-17 |
| JPS6225675B2 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05255090A (en) * | 1991-06-14 | 1993-10-05 | Merck & Co Inc | 1,4-benzodiazepines having a 5-membered heterocyclic ring |
-
1983
- 1983-09-24 JP JP17680083A patent/JPS6067486A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05255090A (en) * | 1991-06-14 | 1993-10-05 | Merck & Co Inc | 1,4-benzodiazepines having a 5-membered heterocyclic ring |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6225675B2 (en) | 1987-06-04 |
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