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公开(公告)号:US5198562A
公开(公告)日:1993-03-30
申请号:US739022
申请日:1991-08-01
CPC分类号: B01J31/2404 , B01J31/2452 , C07C67/31 , C07F15/0053 , B01J2231/643 , B01J2531/821 , B01J31/1805
摘要: A ruthenium-phosphine complex represented by formula (I): ##STR1## wherein R.sup.2 -BINAP represents a teritary phosphine compound represented by formula (II): ##STR2## wherein R.sup.2 represents a hydrogen atom, a methyl group, a methoxy group, or a t-butyl group; X represents a halogen atom; and R and R.sup.1, which may be the same or different, each represent a phenyl group or a substituted phenyl group, and a ruthenium-phosphine complex represented by formula (III): ##STR3## wherein R and R.sup.1 are as defined above; and dma represents N,N-dimethylacetamide, which is an intermediate for synthesizing the ruthenium-phosphine complex of formula (I), are disclosed. The complex of formula (I) is useful as a catalyst for general syntheses with its ligand being an optically inactive compound or for asymmetric syntheses with its ligand being an optically active compound and, also, can be prepared at a low cost.
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2.
公开(公告)号:US5420306A
公开(公告)日:1995-05-30
申请号:US751843
申请日:1991-08-29
IPC分类号: C07D307/33 , B01J31/24 , C07B53/00 , C07B61/00 , C07D315/00 , C07D305/12
CPC分类号: B01J31/2404 , B01J31/24 , B01J31/2452 , C07D315/00 , B01J2231/643 , B01J2531/0216 , B01J2531/0266 , B01J2531/821 , B01J31/1805 , B01J31/2208
摘要: A process for producing an optically active .gamma.-butyrolactone derivative represented by formula (II): ##STR1## wherein R.sup.1 represents an alkyl group having from 1 to 10 carbon atoms or a substituted or unsubstituted phenyl group; and * indicates an asymmetric carbon atom, is disclosed, comprising enantioselectively hydrogenating a .gamma.-keto acid or an ester thereof represented by formula (I): ##STR2## wherein R.sup.1 and * are as defined above; and R.sup.2 represents a hydrogen atom or a lower alkyl group, in the presence of an optically active ruthenium-phosphine complex. The compounds (I) can be obtained at high optical purity through simple operations and a reduced number of steps.
摘要翻译: 制备由式(II)表示的光学活性γ-丁内酯衍生物的方法:其中R 1表示具有1至10个碳原子的烷基或取代或未取代的苯基; 和*表示不对称碳原子,包括对映体氢化由式(I)表示的γ-酮酸或其酯:其中R 1和*如上所定义; 在光学活性钌膦络合物的存在下,R 2表示氢原子或低级烷基。 化合物(I)可以通过简单的操作和减少数量的步骤以高光学纯度获得。
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公开(公告)号:US4962242A
公开(公告)日:1990-10-09
申请号:US66164
申请日:1987-06-25
申请人: Nobuo Yamada , Toshiyuki Takezawa , Noboru Sayo , Misao Yagi , Hidenori Kumobayashi , Susumu Akutagawa , Hidemasa Takaya , Shinichi Inoue , Ryoji Noyori
发明人: Nobuo Yamada , Toshiyuki Takezawa , Noboru Sayo , Misao Yagi , Hidenori Kumobayashi , Susumu Akutagawa , Hidemasa Takaya , Shinichi Inoue , Ryoji Noyori
IPC分类号: C07C29/17
CPC分类号: C07C29/172 , C07B2200/07
摘要: A process for producing an optically active alcohol represented by formula (I): ##STR1## wherein R.sub.1 is an alkyl group having from 2 to 11 carbon atoms, an alkenyl group having from 3 to 11 carbon atoms, an alkadienyl group having from 6 to 11 carbon atoms, a cyclohexyl group, an cyclohexylmethyl group, or a cyclohexylethyl group, provided that the olefin in the alkenyl group or alkadienyl group is not conjugated to the olefin at the 2-position thereof; and * means an asymmetric carbon atom,is disclosed, comprising subjecting an olefinic alcohol represented by formula (II): ##STR2## wherein R.sub.1 is the same as defined above to asymmetric hydrogenation in the presence of, as a catalyst, a ruthenium-optically active phosphine complex.According to the process of the invention, the desired optically active alcohols which are useful not only as intermediates for the manufacture of perfumes and vitamin E but also as liquid crystal materials can be produced with high optical purities.
摘要翻译: 一种制备由式(I)表示的光学活性醇的方法:其中R1是具有2至11个碳原子的烷基,具有3至11个碳原子的链烯基,具有 环己基,环己基甲基或环己基乙基,条件是烯基或链二烯基中的烯烃在2-位没有与烯烃共轭; 和*表示不对称碳原子,包括使式(II)表示的烯属醇:其中R 1与上述定义相同,在作为催化剂的存在下进行不对称氢化 钌 - 光学活性膦配合物。 根据本发明的方法,不仅可用于制造香料和维生素E,而且用作液晶材料的中间体所需的光学活性醇可以以高光学纯度生产。
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公开(公告)号:US5066815A
公开(公告)日:1991-11-19
申请号:US520149
申请日:1990-05-08
IPC分类号: C07D307/33 , B01J31/24 , C07B31/00 , C07B41/02 , C07B53/00 , C07B61/00 , C07C27/00 , C07C29/145 , C07C31/20 , C07C31/36 , C07C33/26 , C07C35/06 , C07C35/08 , C07C41/00 , C07C41/26 , C07C43/13 , C07C43/178 , C07C51/00 , C07C51/367 , C07C59/01 , C07C59/50 , C07C67/00 , C07C67/31 , C07C213/00 , C07C215/08
CPC分类号: C07C29/145 , C07C41/26 , C07C51/367 , C07B2200/07 , C07C2101/08 , C07C2101/14
摘要: A process for preparing an optically active alcohol is disclosed, which comprises asymmetrically hydrogenating a carbonyl compound in the presence of a ruthenium-optically active phosphine complex as a catalyst. The resulting alcohol has high optical purity.
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公开(公告)号:US4739084A
公开(公告)日:1988-04-19
申请号:US38570
申请日:1987-04-15
申请人: Hidemasa Takaya , Tetsuo Ohta , Ryoji Noyori , Nobuo Yamada , Toshiyuki Takezawa , Noboru Sayo , Takanao Taketomi , Hidenori Kumobayashi , Susumu Akutagawa
发明人: Hidemasa Takaya , Tetsuo Ohta , Ryoji Noyori , Nobuo Yamada , Toshiyuki Takezawa , Noboru Sayo , Takanao Taketomi , Hidenori Kumobayashi , Susumu Akutagawa
IPC分类号: B01J31/00 , B01J31/24 , C07B61/00 , C07C29/17 , C07C33/025 , C07C51/36 , C07F15/00 , C07F9/50
CPC分类号: C07F15/0053 , C07C29/17 , C07C33/025 , C07C51/36 , C07B2200/07
摘要: A ruthenium-phosphine complex having a 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl or its derivative as a ligand and carboxyl groups bonded to the ruthenium atom thereof is disclosed. The complex is inexpensive and exhibits excellent performances as a catalyst for various organic syntheses, and particularly for asymmetric hydrogenation.
摘要翻译: 公开了具有2,2'-双(二苯基膦基)-1,1'-联萘或其衍生物作为配体的钌 - 膦配合物和与其钌原子键合的羧基。 该复合物是廉价的并且表现出优异的性能,作为各种有机合成的催化剂,特别是用于不对称氢化。
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公开(公告)号:US4933482A
公开(公告)日:1990-06-12
申请号:US204480
申请日:1988-06-09
申请人: Noboru Sayo , Takao Saito , Hidenori Kumobayashi , Susumu Akutagawa , Ryoji Noyori , Hidemasa Takaya
发明人: Noboru Sayo , Takao Saito , Hidenori Kumobayashi , Susumu Akutagawa , Ryoji Noyori , Hidemasa Takaya
IPC分类号: C07C67/303 , B01J31/24 , C07B31/00 , C07B53/00 , C07B61/00 , C07C67/00 , C07C67/31 , C07C69/675 , C07C69/757 , C07C227/00 , C07C227/16 , C07C227/32 , C07C229/22 , C07C229/24 , C07C231/00 , C07C231/12 , C07C231/18 , C07C235/06 , C07C235/34 , C07C237/06 , C07C325/00 , C07C327/22
CPC分类号: C07C227/32 , C07C323/00
摘要: A process for preparing an optically active alcohol is disclosed, which comprises asymmetrically hydrogenating a .beta.-keto acid derivative in the presence of a ruthenium-optically active phosphine complex as a catalyst. The resulting alcohol has high optical purity.
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公开(公告)号:US4962230A
公开(公告)日:1990-10-09
申请号:US121247
申请日:1987-11-16
申请人: Hidemasa Takaya , Tetsuo Ohta , Ryoji Noyori , Noboru Sayo , Hidenori Kumobayashi , Susumu Akutagawa
发明人: Hidemasa Takaya , Tetsuo Ohta , Ryoji Noyori , Noboru Sayo , Hidenori Kumobayashi , Susumu Akutagawa
CPC分类号: C07F15/0053 , C07C51/36
摘要: A process for producing an optically active carboxylic acid represented by formula (I): ##STR1## wherein R.sup.1, and R.sup.2, and R.sup.3 each represents a hydrogen atom, an alkyl group, an alkenyl group, or a phenyl or naphthyl group which may have a substituent, provided that all of R.sup.1, R.sup.2, and R.sup.3 are not simultaneously a hydrogen atom; when R.sup.1 and R.sup.2 are simultaneously a hydrogen atom, then R.sup.3 is not a methyl group; and that when R.sup.3 is a hydrogen atom, then R.sup.1 and R.sup.2 are each a group other then a hydrogen atom,is disclosed, comprising asymmetrically hydrogenating an .alpha.,.beta.-unsaturated carboxylic acid represented by formula (II): ##STR2## wherein R.sup.1, R.sup.2, and R.sup.3 are the same as defined above, in the presence of a ruthenium-optically active phosphine complex as a catalyst.According to the process of the invention, the desired optically active carboxylic acids which can be widely used as raw materials for synthesizing various useful compounds, for example, as intermediates for synthesizing physiologically active substances of natural materials and also as liquid crystal materials can be industrially advantageously produced.
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公开(公告)号:US4916252A
公开(公告)日:1990-04-10
申请号:US207428
申请日:1988-06-16
申请人: Noboru Sayo , Takao Saito , Hidenori Kumobayashi , Susumu Akutagawa , Ryoji Noyori , Hidemasa Takaya
发明人: Noboru Sayo , Takao Saito , Hidenori Kumobayashi , Susumu Akutagawa , Ryoji Noyori , Hidemasa Takaya
IPC分类号: B01J31/24 , C07B31/00 , C07B41/02 , C07B53/00 , C07B61/00 , C07C27/00 , C07C29/145 , C07C31/20 , C07C31/42 , C07C33/26 , C07C33/46 , C07C35/06 , C07C41/00 , C07C41/26 , C07C43/178 , C07C67/00 , C07C67/31 , C07C69/675 , C07C69/738 , C07C213/00 , C07C215/18 , C07F15/00
CPC分类号: C07C29/145 , C07C41/26 , C07B2200/07 , C07C2101/08 , C07C2101/14
摘要: A process for preparing an optically active alcohol is disclosed, which comprises asymmetrically hydrogenating a 1,3-diketone in the presence of a ruthenium-optically active phosphine complex as a catalyst. The resulting alcohol has high optical purity.
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9.
公开(公告)号:US5631397A
公开(公告)日:1997-05-20
申请号:US470466
申请日:1995-06-06
申请人: Tetsuro Yamasaki , Hidenori Kumobayashi , Noboru Sayo , Toshiyuki Murayama , Noboru Sano , Takero Ishizaki
发明人: Tetsuro Yamasaki , Hidenori Kumobayashi , Noboru Sayo , Toshiyuki Murayama , Noboru Sano , Takero Ishizaki
IPC分类号: B01J31/22 , B01J31/24 , C07B61/00 , C07C215/28 , C07C221/00 , C07C225/16 , C07C231/12 , C07C231/18 , C07C233/36 , C07C233/43 , C07C233/78 , C07C269/06 , C07C271/20
CPC分类号: C07C221/00 , C07C231/12 , C07C231/18 , C07C233/36 , C07C233/78 , C07C269/06 , C07C271/20
摘要: Disclosed herein is a process for producing a (2S,5S)-2,5-diamino-1,6-diphenyl-3-hexanone derivative represented by the formula (1): ##STR1## wherein R.sup.1 means a lower alkylcarbonyl group, a halogen-substituted lower alkylcarbonyl group, an arylcarbonyl group or a lower alkoxycarbonyl group, and R.sup.2 and R.sup.3 are identical with or different from each other and denote individually an aryl group or an alkoxy-substituted aryl group, which comprises subjecting a (2S)-2,5-diamino-1,6-diphenyl-4-hexen-3-one derivative represented by the formula (2): ##STR2## wherein R.sup.1, R.sup.2 and R.sup.3 have the same meaning as defined above, to a hydrogenation reaction in the presence of a transition metal-containing catalyst.
摘要翻译: 本文公开了一种制备由式(1)表示的(2S,5S)-2,5-二氨基-1,6-二苯基-3-己酮衍生物的方法:其中R1表示低级烷基羰基 基团,卤素取代的低级烷基羰基,芳基羰基或低级烷氧基羰基,R 2和R 3彼此相同或不同,分别表示芳基或烷氧基取代的芳基,其包括使( 2S)-2,5-二氨基-1,6-二苯基-4-己烯-3-酮衍生物:其中R1,R2和R3具有与上述相同的含义。 在含过渡金属的催化剂存在下进行氢化反应。
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公开(公告)号:US5502221A
公开(公告)日:1996-03-26
申请号:US437074
申请日:1995-05-05
申请人: Noboru Sayo , Noboru Sano , Hidenori Kumobayashi
发明人: Noboru Sayo , Noboru Sano , Hidenori Kumobayashi
IPC分类号: C07C69/675 , C07C227/32 , C07C229/28 , C07C247/12 , C07D303/48 , C07D303/38
CPC分类号: C07C227/32 , C07C229/28 , C07C247/12 , C07C69/675 , C07D303/48 , C07C2101/14
摘要: A process for for producing a (2R,3S)-cyclohexylnorstatine or a salt thereof is disclosed, which comprises the steps of: enantioselectively hydrogenating a 4-cyclohexyl-2-halogeno-3-oxobutyric acid ester in the presence of a ruthenium-phosphine complex to produce a 4-cyclohexyl-2-halogeno-(3R)-hydroxybutyric acid ester (2); epoxidizing the compound (2) in the presence of a base to produce a 4-cyclohexyl-(2S,3R)-epoxybutyric acid ester (3); reacting the compound (3) with a lower trialkylsilyl azide in the presence of a Lewis acid to produce a (3S)-azide-4-cyclohexyl-(2S)-substituted butyric acid ester (4); subjecting the compound (4) to hydrogenolysis to produce a (2S,3S)-cyclohexylnorstatine derivative (5); and inverting the configuration at the 2-position of the compound (5).
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