公开(公告)号：US06472539B1

公开(公告)日：2002-10-29

申请号：US09899207

申请日：2001-07-06

申请人： Tohru Yokozawa ,  Takao Saito ,  Noboru Sayo ,  Takero Ishizaki

发明人： Tohru Yokozawa ,  Takao Saito ,  Noboru Sayo ,  Takero Ishizaki

IPC分类号： C07F940

CPC分类号： C07F9/65517

摘要： A process for producing a diphosphine oxide or diphosphonate represented by formula (1) as defined, which comprises treating, with a base, a phosphine compound represented by formula (2) as defined and adding the thus-treated phosphine compound to a nonpolar solvent having an oxidative metal compound suspended therein so as to effect dimerization. The present invention makes it possible to produce, conveniently, in a high yield and safely, a diphosphine oxide or diphosphonate which is an intermediate for producing a diphosphine compound useful as a ligand of a metal complex serving as a catalyst for asymmetric synthesis reaction.

摘要翻译： 一种制备由式（1）表示的二膦氧化物或二膦酸盐的方法，该方法包括用碱处理如上定义的式（2）表示的膦化合物，并将如此处理的膦化合物加入到具有 悬浮在其中以实现二聚化的氧化金属化合物。 本发明使得可以以高产率和安全地生产作为用作不对称合成反应催化剂的金属络合物的配位体的二膦化合物的中间体的二氧化膦或二膦酸盐的方法。

公开(公告)号：US06333291B1

公开(公告)日：2001-12-25

申请号：US09698208

申请日：2000-10-30

申请人： Tohru Yokozawa ,  Noboru Sayo ,  Takao Saito ,  Takero Ishizaki

发明人： Tohru Yokozawa ,  Noboru Sayo ,  Takao Saito ,  Takero Ishizaki

IPC分类号： B01J3100

CPC分类号： B01J31/2457 ,  B01J31/2226 ,  B01J31/2295 ,  B01J2231/643 ,  B01J2231/645 ,  B01J2531/0266 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/824 ,  B01J2531/827 ,  B01J2531/847 ,  C07F9/4021 ,  C07F9/5325 ,  C07F9/65527 ,  C07F15/0033 ,  C07F15/004 ,  C07F15/0046 ,  C07F15/0053 ,  C07F15/006 ,  C07F15/0066 ,  C07F15/0073 ,  C07F15/008 ,  C07F15/04 ,  C07F15/045

摘要： This invention provides a novel diphosphine compound which is useful as a ligand of catalysts for asymmetric synthesis reactions, particularly asymmetric hydrogenation reaction. Particularly, it provides a diphosphine compound represented by a general formula (1): wherein R1 and R2 each independently represents a cycloalkyl group, an unsubstituted or substituted phenyl group or a five-membered aromatic heterocycle residue.

摘要翻译： 本发明提供了一种新的二膦化合物，其可用作用于不对称合成反应的催化剂的配体，特别是不对称氢化反应。 特别地，它提供由通式（1）表示的二膦化合物：其中R 1和R 2各自独立地表示环烷基，未取代或取代的苯基或五元芳族杂环残基。

公开(公告)号：US06492545B2

公开(公告)日：2002-12-10

申请号：US09909803

申请日：2001-07-23

申请人： Takao Saito ,  Tohru Yokozawa ,  Kazuhiko Matsumura ,  Noboru Sayo

发明人： Takao Saito ,  Tohru Yokozawa ,  Kazuhiko Matsumura ,  Noboru Sayo

IPC分类号： C07C6966

CPC分类号： C07C67/31 ,  C07B2200/07 ,  Y02P20/55 ,  C07C69/675

摘要： A novel process in which an optically active alcohol compound having a desired absolute configuration and a high optical purity can be obtained by asymmetrically hydrogenating a &bgr;-keto acid compound through a simple operation. An optically active alcohol represented by general formula (III) as defined is obtained by asymmetrically hydrogenating a &bgr;-keto ester compound represented by general formula (I) as defined in the presence of at least one ruthenium complex having as a ligand an optically active tertiary diphosphine compound represented by general formula (II) as defined.

摘要翻译： 通过简单的操作通过不对称氢化β-酮酸化合物，可以获得具有所需绝对构型和高光学纯度的光学活性醇化合物的新方法。 由通式（III）表示的光学活性醇通过不对称氢化由通式（I）表示的β-酮酯化合物获得，如在至少一种具有光学活性第三级 如通式（Ⅱ）所示的二膦化合物。

公开(公告)号：US06313317B1

公开(公告)日：2001-11-06

申请号：US09273260

申请日：1999-03-22

申请人： Noboru Sayo ,  Takao Saito ,  Tohru Yokozawa

发明人： Noboru Sayo ,  Takao Saito ,  Tohru Yokozawa

IPC分类号： C07F930

CPC分类号： B01J31/2457 ,  B01J31/2295 ,  B01J2231/643 ,  B01J2231/645 ,  B01J2531/821 ,  C07B53/00 ,  C07C67/31 ,  C07F15/0053 ,  C07C69/675

摘要： Disclosed is a ruthenium-phosphine complex usable as the catalyst giving a high enantiomer excess in an asymmetric reaction and a method for producing the complex. The ruthenium-phosphine complex is represented by formula (1): [{(RuX(L)}2(&mgr;-X)3]−[R22NH2]+  (1) wherein R2 represents hydrogen, alkyl, cycloalkyl or benzyl and L represents a diphosphine ligand represented by formula (2): wherein R1 represents an optionally substituted phenyl group and X represents a halogen atom. The method for preparing a ruthenium-phosphine complex represented by formula (1) is characterized in that a ruthenium complex represented by the formula [RuX(arene)(L)]X and an ammonium salt represented by the formula R22NH.HX are reacted with each other.

摘要翻译： 公开了可用作在不对称反应中给出高对映体过量的催化剂的钌膦络合物和制备该络合物的方法。 钌膦配合物由式（1）表示：其中R2表示氢，烷基，环烷基或苄基，L表示由式（2）表示的二膦配体：其中R1表示任选取代的苯基，X表示卤素原子 。 由式（1）表示的钌 - 膦配合物的制备方法的特征在于，由式[RuX（芳烃）（L）] X表示的钌络合物和由式R22NH.HX表示的铵盐与 彼此。

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：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：US5847222A

公开(公告)日：1998-12-08

申请号：US918347

申请日：1997-08-26

申请人： Tohru Yokozawa ,  Noboru Sayo ,  Kazuhiko Matsumura ,  Hidenori Kumobayashi

发明人： Tohru Yokozawa ,  Noboru Sayo ,  Kazuhiko Matsumura ,  Hidenori Kumobayashi

IPC分类号： B01J31/22 ,  B01J31/24 ,  C07B53/00 ,  C07B61/00 ,  C07F9/50 ,  C07F15/00 ,  C07F9/52

CPC分类号： C07F15/008 ,  B01J31/2409 ,  C07C29/145 ,  C07F15/004 ,  C07F15/0053 ,  C07F15/0066 ,  C07F9/5027 ,  B01J2231/643 ,  B01J2531/0266 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/824 ,  B01J2531/827 ,  B01J2531/847 ,  C07B2200/07

摘要： The present invention provides a ligand for a novel catalyst superior in such characteristics as selectivity (chemoselectivity and enantioselectivity) and catalytic activity in asymmetric synthesis reactions and a ligand for a novel catalyst effective in an asymmetric hydrogenation reaction in particular. The ligand is an optically active diphosphine compound represented by the following formula: ##STR1## where Ph is a phenyl group, X is a chlorine or bromine atom, and R.sup.1 and R.sup.2 are each an alkyl group having 1 to 3 carbon atoms.

摘要翻译： 本发明提供了一种新型催化剂配位体，其特性如选择性（化学选择性和对映体选择性）以及不对称合成反应中的催化活性以及特别是在不对称氢化反应中有效的新型催化剂配位体。 配位体是由下式表示的光学活性二膦化合物：原子或溴原子，R 1和R 2各自为碳原子数1〜3的烷基。

公开(公告)号：US5693868A

公开(公告)日：1997-12-02

申请号：US740506

申请日：1996-10-30

申请人： Noboru Sayo ,  Xiaoyong Zhang ,  Tatsuya Ohmoto ,  Akifumi Yoshida ,  Tohru Yokozawa

发明人： Noboru Sayo ,  Xiaoyong Zhang ,  Tatsuya Ohmoto ,  Akifumi Yoshida ,  Tohru Yokozawa

IPC分类号： B01J31/24 ,  C07B61/00 ,  C07F9/46 ,  C07F9/50 ,  C07F9/53 ,  C07F9/655 ,  C07F15/00 ,  C07F15/04 ,  C07F9/02

CPC分类号： C07F15/045 ,  C07F15/004 ,  C07F15/0053 ,  C07F15/0066 ,  C07F15/008 ,  C07F9/46 ,  C07F9/5027 ,  C07F9/505 ,  C07F9/509 ,  C07F9/5325 ,  C07F9/65517

摘要： The present invention provides a method for producing novel optically active diphosphine compounds �2,2'-bis(di-substituted phosphino)-1,1'-binaphthyl compounds! having a selectivity (chemoselectivity or enantioselectivity) and catalytic activity different from those of conventional BINAP compounds. In a method of the present invention for producing an optically active diphosphine compound (i.e., 2,2-bis(di-substituted phosphino)-1,1'-binaphthyl), 2,2'-bis(trifluoromethanesulfonyloxy)-1,1'-binaphthyl is reacted, in the presence of a transition metal-phosphine complex, with a phosphineoxide compound represented by the following general formula: A.sub.2 P(O)H wherein A represents a phenyl group; a mono- to tri-substituted phenyl group, wherein each substituent in the substituted phenyl group is individually selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group or a lower halogenated-alkoxy group such that one or more of the substituents may be the same or different; a naphthyl group; a lower-alkyl naphthyl group; or a lower-alkoxy naphthyl group.

摘要翻译： 本发明提供了具有选择性（化学选择性或对映体选择性）和催化活性不同的新的光学活性二膦化合物[2,2'-双（二取代膦基）-1,1'-联萘化合物] 常规BINAP化合物。 在本发明的制备光学活性二膦化合物（即2,2-双（二取代膦基）-1,1'-联萘）的方法中，2,2'-双（三氟甲磺酰氧基）-1,1 在过渡金属 - 膦配合物的存在下，与通式为：A2P（O）H表示的膦氧化物化合物反应，其中A表示苯基; 取代苯基中的每个取代基分别选自卤素原子，低级烷基，低级烷氧基或低级卤代 - 烷氧基，使得一个或多个取代的苯基 更多的取代基可以相同或不同; 萘基; 低级烷基萘基; 或低级烷氧基萘基。

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。

公开(公告)号：US4981992A

公开(公告)日：1991-01-01

申请号：US435877

申请日：1989-11-14

申请人： Noboru Sayo ,  Takao Saito ,  Yoshiki Okeda ,  Hiroyuki Nagashima ,  Hidonori Kumobayashi

发明人： Noboru Sayo ,  Takao Saito ,  Yoshiki Okeda ,  Hiroyuki Nagashima ,  Hidonori Kumobayashi

IPC分类号： B01J31/24 ,  C07B53/00 ,  C07B61/00 ,  C07C231/18 ,  C07C233/47 ,  C07C233/83 ,  C07C235/52 ,  C07C269/06 ,  C07C271/22 ,  C07D205/08

CPC分类号： C07C231/18 ,  C07C233/47 ,  C07C233/83 ,  C07C269/06 ,  C07C271/22 ,  C07D205/08 ,  Y02P20/55

摘要： A process for preparing an optically active 3-hydroxybutanoic acid represented by formula (I): ##STR1## wherein: R.sup.1 represents a protective group of carboxylic acid, andR.sup.2 represents a hydrogen atom; a lower alkyl group which may be substituted with a halogen atom; a lower alkoxy group; a phenyl group which may be substituted with a lower alkyl group or a lower alkoxy group; or a benzyloxy group which may be substituted with a lower alkyl group or a lower alkoxy group,is disclosed, comprising asymmetrically hydrogenating a 3-oxobutanoic acid ester represented by formula (II): ##STR2## wherein R.sup.1 and R.sup.2 are as defined above, in the presence of a ruthenium-optically active phosphine complex as a catalyst. The compound of formula (I) which is useful for synthesizing a 4-acetoxyazetidin-2-one derivative, a useful intermediate for obtaining penem antibiotics, can be prepared economically.