JPS6225677B2 - - Google Patents
Info
- Publication number
- JPS6225677B2 JPS6225677B2 JP17680283A JP17680283A JPS6225677B2 JP S6225677 B2 JPS6225677 B2 JP S6225677B2 JP 17680283 A JP17680283 A JP 17680283A JP 17680283 A JP17680283 A JP 17680283A JP S6225677 B2 JPS6225677 B2 JP S6225677B2
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- asymmetric
- compounds
- group
- compound
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- OFJWFSNDPCAWDK-UHFFFAOYSA-N 2-phenylbutyric acid Chemical compound CCC(C(O)=O)C1=CC=CC=C1 OFJWFSNDPCAWDK-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006717 asymmetric allylation reaction Methods 0.000 description 3
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- -1 allyltin compound Chemical class 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006293 aldehyde allylation reaction Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 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
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- AQTUHJABKZECGA-UHFFFAOYSA-N hept-1-en-4-ol Chemical compound CCCC(O)CC=C AQTUHJABKZECGA-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 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
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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.
光学活性２―フエニル酪酸とジアリル錫ジメト
キサイドを無溶媒またはメタノールやエーテル等
の溶媒中で−100〜120℃の温度範囲で反応させる
ことによつて得られる。 It can be obtained by reacting optically active 2-phenylbutyric acid and diallyltin dimethoxide without a solvent or in a solvent such as methanol or ether at a temperature 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を前記式（）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―ルを得ることでき
る。 As described above, the optically active organotin compound of the present invention can obtain optically active homoallyl alcohol by subjecting an aldehyde or ketone to an asymmetric reaction as shown in the formula () and then hydrolyzing the reaction. 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
金属ナトリウム0.77ｇ（33m mol）とメタノー
ル20mlから調製したナトリウムメトキサイド溶液
にジアリル錫ジブロマイド6.0ｇ（16.6m mol）
を加え、室温で１時間撹拌してジアリル錫ジメト
キサイドを製造し、この反応液に（＋）―２―フ
エニル酪酸（〔α〕２２ Ｄ＋81.9゜，（C2.356，エーテ
ル））5.5ｇ（33m mol）を加え、室温で１時間撹
拌した後減圧下でメタノールを留去し、残渣をジ
クロロメタンに溶かして濾過し、濾液の溶媒を留
去して残渣をジクロロメタン―ヘキサンで再結晶
せしめて、目的物（＋）―ジアリル錫ビス（２―
フエニル酪酸）7.9を得た。（収率90％、〔α〕２３ Ｄ
＋
9.8゜，（C5.0，CH2Cl2）。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（KBr法）を第１図及び第２図に示し
た。（光学活性アリルアルコールの合成剤）
実施例によつて得られた（＋）―ジアリル錫ビ
ス（２―フエニル酪酸）10m molと三フツ化ホウ
素エテラート5m molを含むエーテル溶液20ml
に、ｎ―C3H7CHO20m molを−78℃にて滴下し
て５時間反応させた。反応混合物を0.5N―苛性
ソーダ水溶液30mlで加水分解せしめ、続いて1N
―塩酸溶液、水の順で洗浄した後、硫酸マグネシ
ウムで乾燥し、エーテルを留去して残渣を蒸留す
ると６―ヘプテン―４―オールが46％の収率で得
られた。得られたアルコールは、〔α〕２３ Ｄ＋0.70゜
（C10.2，ベンゼン）であつた。Example 6.0 g (16.6 m mol) of diallyltin dibromide was added to a sodium methoxide solution prepared from 0.77 g (33 m mol) of sodium metal and 20 ml of methanol.
was added and stirred at room temperature for 1 hour to produce diallyltin dimethoxide, and 5.5 g of (+)-2-phenylbutyric acid ([α] 22 D +81.9°, (C2.356, ether)) was added to this reaction solution. After stirring at room temperature for 1 hour, methanol was distilled off under reduced pressure, the residue was dissolved in dichloromethane and filtered, the solvent of the filtrate was distilled off, and the residue was recrystallized from dichloromethane-hexane. , Target (+)-diallyltin bis(2-
phenylbutyric acid) 7.9 was obtained. (Yield 90%, [α] 23 D
+
9.8°, (C5.0, CH 2 Cl 2 ). The nuclear magnetic resonance spectrum (CCl 4 solvent, TMS standard) and infrared absorption spectrum (KBr method) of the target product are shown in Figures 1 and 2. (Synthesizing agent for optically active allyl alcohol) 20 ml of an ether solution containing 10 m mol of (+)-diallyltin bis(2-phenylbutyric acid) obtained in Example and 5 m mol of boron trifluoride etherate.
Then, 20 mmol of n-C 3 H 7 CHO was added dropwise at -78°C and reacted for 5 hours. The reaction mixture was hydrolyzed with 30 ml of 0.5N aqueous sodium hydroxide solution, followed by 1N
- After washing with hydrochloric acid solution and water in that order, drying with magnesium sulfate, distilling off the ether and distilling the residue, 6-hepten-4-ol was obtained in a yield of 46%. The alcohol obtained was [α] 23 D +0.70° (C10.2, benzene).
第１図は実施例によつて得られた（＋）―ジア
リル錫ビス（２―フエニル酪酸）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 (+)-diallyltinbis(2-phenylbutyric acid) 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 |
|---|---|---|---|
| JP17680283A JPS6067488A (en) | 1983-09-24 | 1983-09-24 | Optically active ogranotin compound containing asymmetric group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17680283A JPS6067488A (en) | 1983-09-24 | 1983-09-24 | Optically active ogranotin compound containing asymmetric group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6067488A JPS6067488A (en) | 1985-04-17 |
| JPS6225677B2 true JPS6225677B2 (en) | 1987-06-04 |
Family
ID=16020093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17680283A Granted JPS6067488A (en) | 1983-09-24 | 1983-09-24 | Optically active ogranotin compound containing asymmetric group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6067488A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0390824U (en) * | 1989-07-03 | 1991-09-17 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023209506A1 (en) * | 2022-04-25 | 2023-11-02 | Seastar Chemicals Ulc | Tin containing organometallic compounds |
-
1983
- 1983-09-24 JP JP17680283A patent/JPS6067488A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0390824U (en) * | 1989-07-03 | 1991-09-17 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6067488A (en) | 1985-04-17 |
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