公开(公告)号：US06197996B1

公开(公告)日：2001-03-06

申请号：US08139861

申请日：1993-10-22

申请人： Takanao Taketomi ,  Toshiaki Sakaguchi ,  Hidenori Kumobayashi

发明人： Takanao Taketomi ,  Toshiaki Sakaguchi ,  Hidenori Kumobayashi

IPC分类号： C07C22900

CPC分类号： C07C227/32

摘要： A process for preparing an optically active carnitine ester represented by formula (I): wherein R represents a lower alkyl group; and X represents a halogen atom, is disclosed, comprises asymmetrically hydrogenating a &ggr;-trimethylammonium-3-oxobutanoic ester halide represented by formula (II): wherein R and X are as defined above, in the presence of a ruthenium-optically active phosphine complex as a catalyst. An optically active carnitine ester of any desired isomerism can be obtained through simple operation in high yield at high optical purity. The substrate used is easily available.

摘要翻译： 一种制备由式（I）表示的光学活性肉碱酯的方法：其中R表示低级烷基; 并且X表示卤素原子，包括在钌光学活性膦配合物存在下不对称地氢化由式（II）表示的γ-三甲基铵-3-氧代丁酸酯卤化物：其中R和X如上所定义 作为催化剂。 可以通过在高光学纯度下以高产率的简单操作获得任何所需异构体的光学活性肉碱酯。 使用的基材很容易获得。

公开(公告)号：US5012002A

公开(公告)日：1991-04-30

申请号：US538805

申请日：1990-06-15

申请人： Hidenori Kumobayashi ,  Takanao Taketomi

发明人： Hidenori Kumobayashi ,  Takanao Taketomi

IPC分类号： B01J31/24 ,  C07B53/00 ,  C07B61/00 ,  C07C231/18 ,  C07C233/83 ,  C07F9/50 ,  C07F15/00

CPC分类号： C07F15/0013 ,  C07C231/18 ,  C07F15/0053 ,  C07F9/5027

摘要： 2,2'-Bis[di-(m-tolyl)phosphino]-1,1'-binaphthyl represented by formula (I) is disclosed. ##STR1## The compound of formula (I) is capable of forming a complex with a metal, e.g., ruthenium, rhodium, and palladium, which is extremely important and industrially excellent as a catalyst for various asymmetric synthesis reactions.

公开(公告)号：US4906773A

公开(公告)日：1990-03-06

申请号：US287434

申请日：1988-12-21

申请人： Takanao Taketomi ,  Hidenori Kumobayashi

发明人： Takanao Taketomi ,  Hidenori Kumobayashi

IPC分类号： B01J27/185 ,  B01J27/00 ,  C07B61/00 ,  C07C67/00 ,  C07C227/00 ,  C07C227/18 ,  C07C227/20 ,  C07C227/32 ,  C07C229/22 ,  C07C231/18 ,  C07C269/06

CPC分类号： C07C227/32 ,  C07C231/18 ,  C07C269/06

摘要： A process for preparing optically active threonine is disclosed, which comprises asymmetrically hydrogenating a 2-N-acylaminoacetoacetic ester represented by formula (I): ##STR1## wherein R.sup.1 represents a lower alkyl group, a phenyl group, a phenyl group substituted with a lower alkyl group or a lower alkoxy group, a benzyl group, or a benzyl group substituted with a lower alkyl group or a lower alkoxy group; R.sup.2 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a phenyl group substituted with a lower alkyl group or a lower alkoxy group, a benzyloxy group, or a benzyloxy group substituted with a lower alkyl group or a lower alkoxy group, in the presence of a ruthenium-optically active phosphine complex as a catalyst to obtain an optically active threonine derivative represented by formula (II): ##STR2## wherein R.sup.1 and R.sup.2 are as defined above, and then hydrolyzing the compound of formula (II). The 2-N-acylaminoacetoacetic ester intermediate can be selectively prepared in a high yield. Either natural type threonine or non-natural type threonine can be prepared selectively by selecting the absolute configuration of the ligand of the ruthenium-optically active phosphine complex.

公开(公告)号：US4895979A

公开(公告)日：1990-01-23

申请号：US313007

申请日：1989-02-21

申请人： Ryoji Noyori ,  Masato Kitamura ,  Takeshi Ohkuma ,  Hidenori Kumobayashi

发明人： Ryoji Noyori ,  Masato Kitamura ,  Takeshi Ohkuma ,  Hidenori Kumobayashi

IPC分类号： B01J31/24 ,  B01J31/26 ,  B01J31/28 ,  C07B31/00 ,  C07B53/00 ,  C07B61/00 ,  C07C67/00 ,  C07C67/30 ,  C07C67/31 ,  C07C69/675 ,  C07C227/00 ,  C07C227/08 ,  C07C227/32 ,  C07C229/22

CPC分类号： C07C227/32 ,  C07C229/22

摘要： A process for preparing carnitine which comprises asymmetrically hydrogenating a .gamma.-halogeno-.beta.-keto ester represented by formula (I): ##STR1## wherein X represents a chlorine atom or a bromine atom; and R represents a lower alkyl group, in the presence of a ruthenium-optically active phosphine complex represented by formula (II), (III) or (IV):Ru.sub.2 Cl.sub.4 (L).sub.2 (C.sub.2 H.sub.5).sub.3 N (II)Ru(OCOR.sup.2).sub.2 (L) (IV)RuX.sub.2 (L) (V)wherein L represents 2,2'-bis(di-p-R.sup.1 -phenylphosphino)- 1,1'-binaphthyl of formula (III): ##STR2## wherein R.sup.1 represents a hydrogen atom, a methyl group, or a t-butyl group;R.sup.2 represents a lower alkyl group or a trifluoromethyl group; and X is as defined above,as a catalyst at a temperature of from 70.degree. to 150.degree. C. to obtain an optically active alcohol represented by formula (VI): ##STR3## wherein X and R are as defined above, and then reacting the optically active alcohol as obtained with trimethylamine without isolation, is disclosed.

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。

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).

公开(公告)号：US5523458A

公开(公告)日：1996-06-04

申请号：US229678

申请日：1994-04-19

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 ,  C07C233/01

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。

公开(公告)号：US5442105A

公开(公告)日：1995-08-15

申请号：US175505

申请日：1993-12-30

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 ,  C07C61/08

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).

摘要翻译： 公开了一种制备（2R，3S） - 环己基异腈或其盐的方法，其包括以下步骤：在钌 - 磷化氢存在下对4-选择性氢化4-环己基-2-卤代-3-氧代丁酸酯 复合以制备4-环己基-2-卤代 - （3R） - 羟基丁酸酯（2）; 在碱的存在下使化合物（2）环氧化，得到4-环己基 - （2S，3R） - 环氧丁酸酯（3）; 在路易斯酸存在下使化合物（3）与低级三烷基甲硅烷基叠氮化物反应，得到（3S） - 叠氮-4-环己基 - （2S） - 取代的丁酸酯（4）; 使化合物（4）进行氢解以制备（2S，3S） - 环己基稳定剂衍生物（5）; 并使化合物（5）的2位的构型反转。

公开(公告)号：US5206399A

公开(公告)日：1993-04-27

申请号：US769264

申请日：1991-10-01

申请人： Noboru Sayo ,  Hidenori Kumobayashi

发明人： Noboru Sayo ,  Hidenori Kumobayashi

IPC分类号： B01J23/46 ,  B01J31/24 ,  C07B53/00 ,  C07B61/00 ,  C07C17/354 ,  C07C25/18 ,  C07C25/22 ,  C07C29/17 ,  C07C33/025 ,  C07C231/12 ,  C07C231/18 ,  C07C233/83 ,  C07D333/32 ,  C07F3/02 ,  C07F9/50 ,  C07F9/53 ,  C07F15/00 ,  C07F15/04

CPC分类号： B01J31/2457 ,  C07B53/00 ,  C07C25/22 ,  C07F15/004 ,  C07F15/0053 ,  C07F15/008 ,  C07F9/5027 ,  B01J2231/643 ,  B01J2531/0266 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/827 ,  C07C2102/10

摘要： 2,2'-Bis(diphenylphosphino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl represented by formula (I). ##STR1## is disclosed. A transition metal complex containing the same, a process for producing 2,2'-Bis(diphenylphosphino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl, and a process for producing 2,2'-bis(diphenylphosphinyl)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl are also disclosed.

公开(公告)号：US5808162A

公开(公告)日：1998-09-15

申请号：US683199

申请日：1996-07-18

申请人： Noboru Sayo ,  Xiaoyong Zhang ,  Tatsuya Omoto ,  Tohru Yokozawa ,  Tetsuro Yamasaki ,  Hidenori Kumobayashi

发明人： Noboru Sayo ,  Xiaoyong Zhang ,  Tatsuya Omoto ,  Tohru Yokozawa ,  Tetsuro Yamasaki ,  Hidenori Kumobayashi

IPC分类号： B01J31/24 ,  C07B53/00 ,  C07F9/50 ,  C07F9/53 ,  C07F9/6553 ,  C07F15/00 ,  C07F15/04 ,  C07F5/02 ,  C07D327/00 ,  C07F9/06 ,  C07F9/28

CPC分类号： B01J31/2452 ,  C07B53/00 ,  C07F15/004 ,  C07F15/0053 ,  C07F15/0066 ,  C07F15/008 ,  C07F15/045 ,  C07F9/5027 ,  C07F9/5325 ,  C07F9/655345 ,  B01J2231/643 ,  B01J2531/0266 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/824 ,  B01J2531/827 ,  B01J2531/847

摘要： A novel chiral unsymmetric diphosphine compound of formula (I): ##STR1## wherein Ar.sup.1 and Ar.sup.2, which are different from each other, each represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a furfuryl group, a benzofurfuryl group, a thienyl group, or a benzothienyl group, and a transition metal complex containing the diphosphine compound as a ligand. The complex catalyzes various asymmetric synthesis reactions, e.g., asymmetric hydrogenation or asymmetric hydrosilylation, exhibiting excellent performance in selectivity, conversion and catalytic activity, to provide a product of desired absolute configuration at high optical purity and in high yield.

摘要翻译： 式（I）的新型手性不对称二膦化合物：其中Ar 1和Ar 2彼此不同的各自表示取代或未取代的苯基，取代或未取代的萘基，吡啶基， 喹啉基，异喹啉基，糠基，苯并呋喃基，噻吩基或苯并噻吩基，以及含有二膦化合物作为配体的过渡金属络合物。 络合物催化各种不对称合成反应，例如不对称氢化或不对称氢化硅烷化，在选择性，转化和催化活性方面表现出优异的性能，以高光学纯度和高产率提供所需绝对构型的产物。