JPH01230537A - Production of optically active alcohol - Google Patents
Production of optically active alcoholInfo
- Publication number
- JPH01230537A JPH01230537A JP63056352A JP5635288A JPH01230537A JP H01230537 A JPH01230537 A JP H01230537A JP 63056352 A JP63056352 A JP 63056352A JP 5635288 A JP5635288 A JP 5635288A JP H01230537 A JPH01230537 A JP H01230537A
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- organometallic compound
- group
- olefins
- asymmetric
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- 150000002576 ketones Chemical class 0.000 claims abstract description 17
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 abstract description 10
- 125000000217 alkyl group Chemical group 0.000 abstract description 10
- 230000003287 optical effect Effects 0.000 abstract description 9
- 125000003118 aryl group Chemical group 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 125000000962 organic group Chemical group 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 150000008282 halocarbons Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 1
- QJXCFMJTJYCLFG-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzaldehyde Chemical compound FC1=C(F)C(F)=C(C=O)C(F)=C1F QJXCFMJTJYCLFG-UHFFFAOYSA-N 0.000 description 1
- 238000006596 Alder-ene reaction Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- WVEBQVBMPNXJCK-UHFFFAOYSA-N hexane;trimethylalumane Chemical compound C[Al](C)C.CCCCCC WVEBQVBMPNXJCK-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- YULMNMJFAZWLLN-UHFFFAOYSA-N methylenecyclohexane Chemical compound C=C1CCCCC1 YULMNMJFAZWLLN-UHFFFAOYSA-N 0.000 description 1
- WPHGSKGZRAQSGP-UHFFFAOYSA-N methylenecyclohexane Natural products C1CCCC2CC21 WPHGSKGZRAQSGP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000005309 thioalkoxy group Chemical group 0.000 description 1
- 125000005296 thioaryloxy group Chemical group 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はアルデヒドあるいは非対称ケトンをオレフィン
類に挿入付加することにより、光学活性アルコールを製
造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing optically active alcohols by inserting and adding aldehydes or asymmetric ketones to olefins.
［従来の技術］
光学活性アルコールの製造法は、学術上、工業上非常に
重要である。従来より、光学活性アルコールを効率よく
製造する方法が神々検討されており、例えば、不斉合成
、光学分割、酸素利用等の方法の検討が行なわれている
。（例えば、「不斉合成と光学分割の進歩」大塚、向山
編、化学同人（１９８２）、ｒ Ｅｎｚｙｍｅｓ ｉｎ
ｏｒｇａｎｉｃ ５ｙｎｔｈｅｓｉｓｉＪ Ｃ１ｂａ
Ｆｏｕｎｄａｔｉｏｎ ｓｙｍｐｏｓｉｕｍ ｍ、 Ｐ
ｉｔ＊ａｎ （１９８５）参照）。[Prior Art] Methods for producing optically active alcohols are of great academic and industrial importance. Conventionally, methods for efficiently producing optically active alcohols have been studied, and methods such as asymmetric synthesis, optical resolution, and oxygen utilization have been investigated. (For example, "Advances in asymmetric synthesis and optical resolution" edited by Otsuka and Mukaiyama, Kagaku Dojin (1982), r Enzymes in
organic 5ynthesisiJ C1ba
Foundation symposium m, P
(see it*an (1985)).
しかしながら、従来技術では（１）化学収率や化学収率
が低い（２）反応条件の制御が困難（３）多量の反応触
媒が必要（４）スケールアップが困難などの実用上の難
点を伴うことが多かった。それゆえ実用的な光学活性ア
ルコールの製造法の発明が強く望まれていた。However, conventional techniques involve practical difficulties such as (1) low chemical yield and chemical yield, (2) difficulty in controlling reaction conditions, (3) need for a large amount of reaction catalyst, and (4) difficulty in scaling up. There were many things. Therefore, the invention of a practical method for producing optically active alcohols has been strongly desired.
［課題を解決するための手段］
本発明者は上記問題点を解決すべく検討を行ない、新規
な光学活性アルコールの製造法を提供するに至った。す
なわち、本発明は、有機金属化合物の存在下にアルデヒ
ドまたは非対称ケトンをオレフィン類に挿入付加するこ
とを特徴とする光学活性アルコールの製造法である。[Means for Solving the Problems] The present inventors have conducted studies to solve the above-mentioned problems, and have now provided a novel method for producing optically active alcohols. That is, the present invention is a method for producing an optically active alcohol, which is characterized by inserting and adding an aldehyde or an asymmetric ketone to an olefin in the presence of an organometallic compound.
アルデヒドまたは非対称ケトンをオレフィン類に挿入付
加する反応は、エン反応と呼ばれ公知である（Ｇ、Ｉｌ
、Ｇ１１ｌ らＪ、 Ｃｈｅｗ、 Ｓｏｃ、Ｐｅｒｋ
ｉｎＴｒａｎｓ Ｉ、２９４，３１５．３３１１９８４
）参照）、シかし、この反応に光学活性なルイス酸を用
いて、光学活性アルコールの製造に用いた例はない０本
発明では有機金属化合物特に光学活性な有機アルミニウ
ム化合物をルイス酸触媒として用いることにより、アル
デヒドまたは非対称ケトンをオレフィン類に挿入付加す
る反応が円滑に進行することを見出し、しかも、高い光
学収率で光学活性アルコールを製造できることを発見し
た。The reaction of inserting and adding aldehydes or asymmetric ketones to olefins is known as the ene reaction (G, Il
, G11l et al. J. Chew, Soc, Perk.
inTrans I, 294, 315.3311984
), but there is no example of using an optically active Lewis acid in this reaction to produce an optically active alcohol. In the present invention, an organometallic compound, especially an optically active organoaluminum compound, is used as a Lewis acid catalyst. The inventors have discovered that by using this method, the intercalation-addition reaction of aldehydes or asymmetric ketones to olefins proceeds smoothly, and that optically active alcohols can be produced with high optical yields.
本発明においては、種々のアルデヒドまたは非対称ケト
ンを基質として用いることか可能であり、これらと多様
なオレフィン類を反応することにより、非常に多くの光
学活性アルコールを製造できる０本発明により製造でき
る化合物は、化学工業における薬品、原材料、あるいは
医薬、農薬、食品またはそれらの中間体などとして有用
である。In the present invention, it is possible to use various aldehydes or asymmetric ketones as substrates, and by reacting these with various olefins, a large number of optically active alcohols can be produced.Compounds that can be produced by the present invention is useful as a drug or raw material in the chemical industry, or as a medicine, agrochemical, food, or an intermediate thereof.
有機金属化合物は、通常触媒量から過剰量が用いられる
。基質であるアルデヒドあるいは非対称ケトンに対して
約０．０１〜１０当景が適切であり、好ましくは約０．
１〜１．５当量使用される。The organometallic compound is usually used in a catalytic amount to an excess amount. For the substrate aldehyde or asymmetric ketone, a range of about 0.01 to 10 is suitable, preferably about 0.
1 to 1.5 equivalents are used.
有機金属化合物としては、光学活性な有機金属化合物が
適当であり、とりわけ光学活性な有機アルミニウム化合
物であることが好ましい。As the organometallic compound, an optically active organometallic compound is suitable, and an optically active organoaluminum compound is particularly preferable.
（Ｒ）
（Ｓ）
上記式（１）、（２）において、上記式（１）、（２）
においてＲＩＪ３はアリール基、アルキル基あるいはア
ルアルキル基を表わし、好ましくはアリール基、特に好
ましくはフェニル基を表わす １１．Ｒ４はアルキル基
、アルアルキル基あるいはアリール基を表わし、好まし
くは低級アルキル基、特に好ましくはメチル基を表わす
。(R) (S) In the above formulas (1) and (2), the above formulas (1) and (2)
11. In, RIJ3 represents an aryl group, an alkyl group or an aralkyl group, preferably an aryl group, and particularly preferably a phenyl group. R4 represents an alkyl group, an aralkyl group or an aryl group, preferably a lower alkyl group, particularly preferably a methyl group.
（１）および（２）の製造法は山水らＪ、＾−０Ｃｈｅ
ｗ、 Ｓｏｃ、、１１０．３１０（１９８８）により知
られている。（１）あるいは（２）を使い分けることに
より光学対掌体を高い光学収率で製造することができる
。 オレフィン類は不飽和二重結合を少なくとも１個有
するオレフィンや、その誘導体（例えば不活性な官能基
を有するオレフィン）であり、特に、不飽和二重結合に
隣接する炭素に少なくとも１個の水素原子を有するオレ
フィンが好ましい、このオレフィンとしては下記式（３
）で表わされる化合物が好ましい。The manufacturing method of (1) and (2) is described by Sansui et al. J, ^-0Che.
W, Soc, 110.310 (1988). Optical antipodes can be produced with high optical yields by selectively using (1) or (2). Olefins are olefins having at least one unsaturated double bond or derivatives thereof (for example, olefins having an inert functional group), and especially those having at least one hydrogen atom on the carbon adjacent to the unsaturated double bond. Preferably, this olefin has the following formula (3
) are preferred.
Ｒ８Ｒ８ＲＩＯ
上記式（３）において、Ｒ１〜ＲＩＧは異なっていても
同一であワてもよく、それは水素原子、アルキル基、ア
リール基、アルアルキル基、ハロゲン原子、アルコキシ
基、アリーロキシ基、アシ豐キシ基、チオアルコキシ基
、チオアリーロキシ基、アルキルアミノ基、アリールア
ミノ基、アシルアミノ基、等を表わし、これらの基は、
他の不活性な官能基を有していてもよい。R8R8RIO In the above formula (3), R1 to RIG may be different or the same, and are hydrogen atoms, alkyl groups, aryl groups, aralkyl groups, halogen atoms, alkoxy groups, aryloxy groups, acyloxy group, thioalkoxy group, thioaryloxy group, alkylamino group, arylamino group, acylamino group, etc., and these groups are
It may also have other inert functional groups.
アルキル基は直鎖状あるいは、分岐状のアルキル基はも
ちろん、シクロアルキル基であつてもよい、また、Ｈｓ
、Ｈｔｏのうちいずれかの基が他のいずれかの基と環を
形成していてもよい。The alkyl group may be a linear or branched alkyl group, as well as a cycloalkyl group, and Hs
, Hto may form a ring with any other group.
オレフィンの炭素数は特に限定されないが、約３０以下
が好ましい、上記アルデヒドあるいは非対称ケトンに対
する、オレフィン類の使用暖は、アルデヒドあるいは非
対称ケトン１当量に対し約１〜５０当量が適当であり、
特に約１〜５当量が好ましい、これらアルデヒドあるい
は非対称ケトンとしては下記式（４）で表わされる化合
物が好ましい。The number of carbon atoms in the olefin is not particularly limited, but it is preferably about 30 or less. The appropriate amount of olefin used for the aldehyde or asymmetric ketone is about 1 to 50 equivalents per equivalent of the aldehyde or asymmetric ketone.
The aldehyde or asymmetric ketone, which is particularly preferably about 1 to 5 equivalents, is preferably a compound represented by the following formula (4).
ＲＩＩｃｏ−Ｒ” −−−（４）式（４）におい
て、Ｒ目とＲ１１は一方が有機基であり、他方が有機基
あるいは水素原子であり、かつ両方が有機基の場合異な
る有機基を表わす、以下仮にＲ１１と有機基とし、Ｒ１
２を第２の有機基あるいは水素原子とする Ｒ１１とし
ては、少なくとも１個のハロゲン原子を有するアルキル
基、アリール基、シクロアルキル基が好ましく、特にハ
ロゲン原子がα位に存在するハロゲン化炭化水素基が好
ましい、この有機基の炭素数は、特に限定されないが、
炭素数１２以下、特に１〜８が好ましい、特に好ましい
Ｒ１１はパーハロアルキル基やパー八ロアリール基等の
水素原子のすべてがハロゲン原子にｌｆｆ１されたハロ
ゲン化炭化水素基である。ハロゲン原子としては塩素原
子とフッ素原子が好ましい。RIIco-R” --- (4) In formula (4), one of the R eyes and R11 is an organic group, the other is an organic group or a hydrogen atom, and when both are organic groups, they represent different organic groups. , below, let R11 be an organic group, and R1
R11 in which 2 is a second organic group or a hydrogen atom is preferably an alkyl group, an aryl group, or a cycloalkyl group having at least one halogen atom, particularly a halogenated hydrocarbon group in which a halogen atom is present at the α-position. is preferable, and the number of carbon atoms in this organic group is not particularly limited, but
Particularly preferred R11 is a halogenated hydrocarbon group having 12 or less carbon atoms, particularly preferably 1 to 8 carbon atoms, in which all hydrogen atoms are converted to halogen atoms, such as a perhaloalkyl group or a peroctaloaryl group. As the halogen atom, a chlorine atom and a fluorine atom are preferred.
）’（１１は、水素原子またはＲ１１と異なる有機基で
あり、特に水素原子が好ましい、Ｒ目が有Ｐｓｆ！の場
合、アルキル基、アリール基、シクロアルキル基等の炭
化水素基やＲ１１とは異なるハロゲン化炭化水素基が好
ましい、Ｒ１２がハロゲン化炭化水素基の場合、ハロゲ
ン原子はα位に存在しないほうが好ましく、また、ハロ
ゲン原子の数もＲ１１より少ないほうが好ましい。)'(11 is a hydrogen atom or an organic group different from R11, and a hydrogen atom is particularly preferable. When R is Psf!, R11 is a hydrocarbon group such as an alkyl group, an aryl group, or a cycloalkyl group. A different halogenated hydrocarbon group is preferable. When R12 is a halogenated hydrocarbon group, it is preferable that the halogen atom is not present at the α-position, and it is also preferable that the number of halogen atoms is smaller than R11.
アルデヒドあるいは非対称ケトンをオレフィン類に挿入
付加して、光学活性アルコールが得られる。即ち、前記
式（４）で表わされるアルデヒドあるいは非対称ケトン
と前記式（３）で表わされるオレフィン類より、下記式
（５）で表わされる生成物が生じる。Optically active alcohols are obtained by intercalative addition of aldehydes or asymmetric ketones to olefins. That is, the product represented by the following formula (5) is produced from the aldehyde or asymmetric ketone represented by the above formula (4) and the olefin represented by the above formula (3).
Ｒ６〜ＲＩｌｌは前記と同じ Ｃ１ｌで示した炭素はア
ルデヒドあるいは非対称ケトンのカルボニル炭素に由来
するものであり、オレフィン類の挿入付加により光学活
性な炭素となる。光学的に対称な有機アルミニウム化合
物を使い分けることにより光学対常体を製造することが
できる。R6 to RIll are the same as above. The carbon represented by C1l is derived from the carbonyl carbon of an aldehyde or an asymmetric ketone, and becomes an optically active carbon by insertion and addition of an olefin. Optical objects can be produced by selectively using optically symmetric organoaluminum compounds.
また、モレキュラーシーブを有機金属化合物と併用して
もよい、モレキュラーシーブは、通常、３Ａ、 ４Ａ、
５Ａ、 １３Ｘなどが用いられるが、特ニ４Ａが好ま
しい、形状は粉末が好ましい、モレキュラーシーブの使
用量は、基質であるアルデヒドあるいは非対称ケトン１
■ｌｏｌに対し、１−１０００■ｇ用いられるが、特に
１０〜２００１ｇが好ましい。In addition, molecular sieves may be used in combination with organometallic compounds, and molecular sieves are usually 3A, 4A,
5A, 13X, etc. are used, but 4A is particularly preferable. The powder form is preferable. The amount of molecular sieve used depends on the substrate aldehyde or asymmetric ketone 1
1 to 1000 g is used per lol, and 10 to 2001 g is particularly preferred.
反応は無溶媒中でも行いうるが、通常不活性な溶媒中で
行われる。溶媒としてはハロゲン化炭化水素系溶媒、炭
化水素系溶媒、エーテル系溶媒などを使用しつる。特に
ジクロロメタンやジクロロエタンなどのハロゲン化炭化
水素系溶媒が好ましい０反応温度は約−１５０〜５０℃
を採用することができ、特に約−１００〜５℃の温和な
条件下で行うことが好ましい。Although the reaction can be carried out without a solvent, it is usually carried out in an inert solvent. As the solvent, halogenated hydrocarbon solvents, hydrocarbon solvents, ether solvents, etc. are used. In particular, halogenated hydrocarbon solvents such as dichloromethane and dichloroethane are preferred.The reaction temperature is approximately -150 to 50°C.
It is particularly preferable to carry out the reaction under mild conditions of about -100 to 5°C.
以下本発明を実施例により具体的に説明するが、本発明
はこれら実施例に限られるものではない。EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.
実施例
イ（表側 １−（２−ヒドロキシ−２−ペンタフルオロ
フェニルエチル）−１−シクロヘキセン（Ｒ） −（＋
）−３，３゛−ビス（トリフェニルシリル）ビナフトー
ル８８層ｇを無水ジクロロメタン３■ｌに溶解し、アル
ゴン雰囲気下０．５Ｍトリメチルアルミニウムーヘキサ
ン溶液０．２２＋ｅｌを室温で加え、さらに室温で１０
０分間撹拌した。この溶液を一２０℃に冷却し、メチレ
ンシクロヘキサン、１９．２＊ｇ％続いてペンタフルオ
ロベンズアルデヒド１９．６ｍｇを同温で滴下し、さら
に４５分間撹拌した。その後、希塩酸水溶液で処理しジ
クロロメタン抽出を行い、生成物をカラムクロマトグラ
フィーにより精製して、表題化合物を１２．３１ｇ（収
率４２％）得た。Example A (front side 1-(2-hydroxy-2-pentafluorophenylethyl)-1-cyclohexene (R) -(+
)-3,3゛-bis(triphenylsilyl)binaphthol (88 g) was dissolved in 3 l of anhydrous dichloromethane, 0.22 + el of 0.5 M trimethylaluminum-hexane solution was added at room temperature under an argon atmosphere, and further 10 g of
Stirred for 0 minutes. This solution was cooled to -20°C, methylene cyclohexane (19.2*g%), followed by 19.6 mg of pentafluorobenzaldehyde were added dropwise at the same temperature, and the mixture was further stirred for 45 minutes. Thereafter, the mixture was treated with a dilute aqueous hydrochloric acid solution and extracted with dichloromethane, and the product was purified by column chromatography to obtain 12.31 g (yield: 42%) of the title compound.
’ＩＩ−ＮＭＲ（ＣＤＣ１ｉｌ ： δ５．０３ （Ｉ
Ｈ） 、 ５．４３ （１旧［α］ ２５ｏ ： ＋
６６．８°（Ｃ１，０，ＣｌＩＣ１＊）生成物をＭ Ｔ
Ｐ Ａ化し、ＨＰＬＣで分析したところ、その光学収
率は８６％ｅｅであった０代表例と同様の操作で光学活
性アルコールを得た。'II-NMR (CDC1il: δ5.03 (I
H), 5.43 (1 old [α] 25o: +
66.8°(C1,0,ClIC1*) product M T
When PA was converted and analyzed by HPLC, the optical yield was 86% ee. An optically active alcohol was obtained in the same manner as in Representative Example 0.
結果を表１にまとめた。The results are summarized in Table 1.
表１
本有機アルミニウムの使用量は特に指定しない場合１１
０ｓｏ１％を用いた。Table 1 The usage amount of this organoaluminum is unless specified otherwise11
0so1% was used.
傘卓モレキュラーシーブ４Ａ（粉末）を併用した。Umbrella Molecular Sieve 4A (powder) was also used.
代臥σ理士ン平石判子Hiraishi Hanko
Claims (5)
対称ケトンをオレフィン類に挿入付加することを特徴と
する光学活性アルコールの製造法。(1) A method for producing an optically active alcohol, which comprises inserting and adding an aldehyde or an asymmetric ketone to an olefin in the presence of an organometallic compound.
個のハロゲン原子を有する、請求項１記載の方法。(2) At least one aldehyde or asymmetric ketone
2. The method of claim 1, having halogen atoms.
る、請求項１記載の方法。(3) The method according to claim 1, wherein the organometallic compound is an optically active organometallic compound.
合物である、請求項１記載の方法。(4) The method according to claim 1, wherein the organometallic compound is an optically active organoaluminum compound.
項１記載の方法。(5) The method according to claim 1, wherein the reaction is carried out in the presence of molecular sieves.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63056352A JPH01230537A (en) | 1988-03-11 | 1988-03-11 | Production of optically active alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63056352A JPH01230537A (en) | 1988-03-11 | 1988-03-11 | Production of optically active alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01230537A true JPH01230537A (en) | 1989-09-14 |
Family
ID=13024840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63056352A Pending JPH01230537A (en) | 1988-03-11 | 1988-03-11 | Production of optically active alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01230537A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009144906A1 (en) * | 2008-05-26 | 2009-12-03 | 高砂香料工業株式会社 | Aluminum complex and use thereof |
-
1988
- 1988-03-11 JP JP63056352A patent/JPH01230537A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009144906A1 (en) * | 2008-05-26 | 2009-12-03 | 高砂香料工業株式会社 | Aluminum complex and use thereof |
| CN102046572A (en) * | 2008-05-26 | 2011-05-04 | 高砂香料工业株式会社 | Aluminum complex and use thereof |
| US8329930B2 (en) | 2008-05-26 | 2012-12-11 | Takasago International Corporation | Aluminum complex and use thereof |
| JP5432895B2 (en) * | 2008-05-26 | 2014-03-05 | 高砂香料工業株式会社 | Aluminum complexes and their use |
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