公开(公告)号：US5606052A

公开(公告)日：1997-02-25

申请号：US436812

申请日：1995-05-08

申请人： Takao Saito ,  Hidenori Kumobayashi ,  Shunichi Murahashi

发明人： Takao Saito ,  Hidenori Kumobayashi ,  Shunichi Murahashi

IPC分类号： B01J27/128 ,  B01J31/12 ,  B01J31/30 ,  C07B61/00 ,  C07D205/08 ,  C07F7/18

CPC分类号： C07F7/186 ,  C07D205/08 ,  C07F7/1892

摘要： A process for preparing a 4-acyloxyazetidinone or a derivative thereof represented by formula (IV): ##STR1## wherein R.sup.1 represents a hydrogen atom, a lower alkyl group, a hydroxyethyl group, or a protected hydroxyethyl group; R.sup.3 represents an alkyl group having from 1 to 10 carbon atoms which may be substituted with a halogen atom, a cyano group, a lower alkoxy group or a phenyl group, or a substituted or unsubstituted phenyl group, provided that the .alpha.-positioned carbon atom of said alkyl group should not have more than two halogen atoms; and R.sup.4 represents a hydrogen atom, a lower alkyl group, or a lower alkoxycarbonyl group, which is useful as an intermediate for penem antibiotics is disclosed, comprising reacting azetidinone or a derivative thereof represented by formula (II): ##STR2## wherein R.sup.1 is as defined above, and R.sup.2 represents a hydrogen atom, a lower alkyl group, a lower alkoxycarbonyl group, or a carboxyl group, with a carboxylic acid represented by formula (III):R.sup.3 COOH (III)wherein R.sup.3 is as defined above, in the presence of (1) a transition metal compound selected from a ruthenium compound, an osmium compound, and a cobalt compound, (2) an aldehyde having 2 or more carbon atoms, provided that the carbon atom at the .alpha.-position thereof should not have two or more halogen atoms, and (3) oxygen. The compound (IV) can be prepared with safety through simple and easy operations.

摘要翻译： 制备由式（Ⅳ）表示的4-酰氧基氮杂环丁酮或其衍生物的方法：原子，低级烷基，羟乙基或被保护的羟乙基; R3表示可以被卤素原子，氰基，低级烷氧基或苯基取代的具有1至10个碳原子的烷基或取代或未取代的苯基，条件是α-位置的碳原子 的所述烷基不应具有多于两个的卤素原子; 其中R 4表示可用作Penem抗生素中间体的氢原子，低级烷基或低级烷氧基羰基，包括使由式（II）表示的氮杂环丁酮或其衍生物： 其中R 1如上所定义，R 2表示氢原子，低级烷基，低级烷氧基羰基或羧基，与式（III）表示的羧酸：R3COOH（III）其中R3如上定义 在（1）选自钌化合物，锇化合物和钴化合物的过渡金属化合物的存在下，（2）具有2个或更多个碳原子的醛，条件是其α位上的碳原子 不应该有两个或更多的卤素原子，和（3）氧。 化合物（IV）可以通过简单和容易的操作安全地制备。

公开(公告)号：US5440030A

公开(公告)日：1995-08-08

申请号：US167201

申请日：1993-12-16

申请人： Takao Saito ,  Hidenori Kumobayashi ,  Shunichi Murahashi

发明人： Takao Saito ,  Hidenori Kumobayashi ,  Shunichi Murahashi

IPC分类号： B01J27/128 ,  B01J31/12 ,  B01J31/30 ,  C07B61/00 ,  C07D205/08 ,  C07F7/18 ,  C07B41/12

CPC分类号： C07F7/186 ,  C07D205/08 ,  C07F7/1892

摘要： A process for preparing a 4-acyloxyazetidinone or a derivative thereof represented by formula (IV): ##STR1## wherein R.sup.1 represents a hydrogen atom, a lower alkyl group, a hydroxyethyl group, or a protected hydroxyethyl group; R.sup.3 represents an alkyl group having from 1 to 10 carbon atoms which may be substituted with a halogen atom, a cyano group, a lower alkoxy group or a phenyl group, or a substituted or unsubstituted phenyl group, provided that the .alpha.-positioned carbon atom of said alkyl group should not have more than two halogen atoms; and R.sup.4 represents a hydrogen atom, a lower alkyl group, or a lower alkoxycarbonyl group,which is useful as an intermediate for penera antibiotics is disclosed, comprising reacting azetidinone or a derivative thereof represented by formula (II): ##STR2## wherein R.sup.1 is as defined above, and R.sup.2 represents a hydrogen atom, a lower alkyl group, a lower alkoxycarbonyl group, or a carboxyl group,with a carboxylic acid represented by formula (III):R.sup.3 COOH (III)wherein R.sup.3 is as defined above,in the presence of (1) a transition metal compound selected from a ruthenium compound, an osmium compound, and a cobalt compound, (2) an aldehyde having 2 or more carbon atoms, provided that the carbon atom at the .alpha.-position thereof should not have two or more halogen atoms, and (3) oxygen. The compound (IV) can be prepared with safety through simple and easy operations.

摘要翻译： 制备由式（IV）表示的4-酰氧基氮杂环丁酮或其衍生物的方法：n原子，低级烷基，羟乙基或被保护的羟乙基; R3表示可以被卤素原子，氰基，低级烷氧基或苯基取代的具有1至10个碳原子的烷基或取代或未取代的苯基，条件是α-位置的碳原子 的所述烷基不应具有多于两个的卤素原子; 其中R 4表示氢原子，低级烷基或低级烷氧基羰基，其可用作倍他安抗生素的中间体，包括使由式（II）表示的氮杂环丁酮或其衍生物： 其中R 1如上所定义，R 2表示氢原子，低级烷基，低级烷氧基羰基或羧基，与式（III）表示的羧酸：R3COOH（III）其中R3如上定义 在（1）选自钌化合物，锇化合物和钴化合物的过渡金属化合物的存在下，（2）具有2个或更多个碳原子的醛，条件是其α位上的碳原子 不应该有两个或更多的卤素原子，和（3）氧。 化合物（IV）可以通过简单和容易的操作安全地制备。

公开(公告)号：US5191076A

公开(公告)日：1993-03-02

申请号：US799150

申请日：1991-11-26

申请人： Takao Saito ,  Hidenori Kumobayashi ,  Shunichi Murahashi

发明人： Takao Saito ,  Hidenori Kumobayashi ,  Shunichi Murahashi

IPC分类号： C07D205/08 ,  B01J23/46 ,  B01J27/08 ,  C07B61/00 ,  C07D205/085

CPC分类号： C07D205/085

摘要： A process for producing a 4-acetoxyazetidinone represented by formula (I): ##STR1## wherein Z represents a hydrogen atom, a lower alkyl group, or a protected or unprotected hydroxyethyl group; and W represents a hydrogen atom, a lower alkyl group, or a group of --COOR.sup.1, wherein R.sup.1 represents a lower alkyl group, is disclosed, which comprises reacting an azetidinone represented by formula (II): ##STR2## wherein Z is as defined above; and Y represents a hydrogen atom, carboxyl group, a lower alkyl group, or a group of --COOR.sup.1, wherein R.sup.1 represents a lower alkyl group, with acetic acid and an oxidizing agent in the presence of, as a catalyst, an anhydrous or hydrous osmium compound represented by OsX.sub.3, wherein X represents a chlorine atom, a bromine atom, or an iodine atom.

公开(公告)号：US5210315A

公开(公告)日：1993-05-11

申请号：US779529

申请日：1991-10-18

申请人： Takao Saito ,  Hidenori Kumobayashi ,  Shunichi Murahashi

发明人： Takao Saito ,  Hidenori Kumobayashi ,  Shunichi Murahashi

IPC分类号： C07C45/28 ,  C07C45/30 ,  C07C49/245 ,  C07C49/337 ,  C07C49/493 ,  C07C49/497 ,  C07C49/503 ,  C07C49/713 ,  C07C49/747 ,  C07C49/82 ,  C07C67/29 ,  C07C67/313 ,  C07D303/16 ,  C07J9/00 ,  C07J71/00

CPC分类号： C07J71/001 ,  C07C45/28 ,  C07C45/30 ,  C07C49/245 ,  C07C49/337 ,  C07C49/493 ,  C07C49/497 ,  C07C49/503 ,  C07C49/713 ,  C07C49/747 ,  C07C49/82 ,  C07C67/29 ,  C07C67/313 ,  C07D303/16 ,  C07J9/00

摘要： A process for producing an .alpha.-hydroxyketone represented by formula (I): ##STR1## wherein R.sup.1 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or an alkoxycarbonyl group; and R.sup.2 and R.sup.3 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aralkyl group, provided that they do not simultaneously represent a hydrogen atom; or a pair of R.sup.1 and R.sup.2, a pair of R.sup.1 and R.sup.3, or a pair of R.sup.2 and R.sup.3 is taken together to form a ring; and the pair of R.sup.1 and R.sup.2 and the pair of R.sup.2 and R.sup.3 may form a ring simultaneously, is disclosed, comprising reacting a compound represented by formula (II): ##STR2## wherein R.sup.1, R.sup.2, and R.sup.3 are as defined above, with an oxidizing agent in the presence of a ruthenium compound and water. .alpha.-Hydroxyketones useful as physiologically active substances are produced with good selectivity and in high yield.

公开(公告)号：US5629420A

公开(公告)日：1997-05-13

申请号：US436810

申请日：1995-05-08

申请人： Takao Saito ,  Hidenori Kumobayashi ,  Shunichi Murahashi

发明人： Takao Saito ,  Hidenori Kumobayashi ,  Shunichi Murahashi

IPC分类号： B01J27/128 ,  B01J31/12 ,  B01J31/30 ,  C07B61/00 ,  C07D205/08 ,  C07F7/18 ,  C07B41/12

CPC分类号： C07F7/186 ,  C07D205/08 ,  C07F7/1892

摘要： A process for preparing a 4-acyloxyazetidinone or a derivative thereof represented by formula (IV): ##STR1## wherein R.sup.1 represents a hydrogen atom, a lower alkyl group, a hydroxyethyl group, or a protected hydroxyethyl group; R.sup.3 represents an alkyl group having from 1 to 10 carbon atoms which may be substituted with a halogen atom, a cyano group, a lower alkoxy group or a phenyl group, or a substituted or unsubstituted phenyl group, provided that the .alpha.-positioned carbon atom of said alkyl group should not have more than two halogen atoms; and R.sup.4 represents a hydrogen atom, a lower alkyl group, or a lower alkoxycarbonyl group, which is useful as an intermediate for penem antibiotics is disclosed, comprising reacting azetidinone or a derivative thereof represented by formula (II): ##STR2## wherein R.sup.1 is as defined above, and R.sup.2 represents a hydrogen atom, a lower alkyl group, a lower alkoxycarbonyl group, or a carboxyl group, with a carboxylic acid represented by formula (III):R.sup.3 COOH (III)wherein R.sup.3 is as defined above, in the presence of (1) a transition metal compound selected from a ruthenium compound, an osmium compound, and a cobalt compound, (2) an aldehyde having 2 or more carbon atoms, provided that the carbon atom at the .alpha.-position thereof should not have two or more halogen atoms, and (3) oxygen. The compound (IV) can be prepared with safety through simple and easy operations.

摘要翻译： 制备由式（Ⅳ）表示的4-酰氧基氮杂环丁酮或其衍生物的方法：原子，低级烷基，羟乙基或被保护的羟乙基; R3表示可以被卤素原子，氰基，低级烷氧基或苯基取代的具有1至10个碳原子的烷基或取代或未取代的苯基，条件是α-位置的碳原子 的所述烷基不应具有多于两个的卤素原子; 其中R 4表示可用作Penem抗生素中间体的氢原子，低级烷基或低级烷氧基羰基，包括使由式（II）表示的氮杂环丁酮或其衍生物： 其中R 1如上所定义，R 2表示氢原子，低级烷基，低级烷氧基羰基或羧基，与式（III）表示的羧酸：R3COOH（III）其中R3如上定义 在（1）选自钌化合物，锇化合物和钴化合物的过渡金属化合物的存在下，（2）具有2个或更多个碳原子的醛，条件是其α位上的碳原子 不应该有两个或更多的卤素原子，和（3）氧。 化合物（IV）可以通过简单和容易的操作安全地制备。

公开(公告)号：US5288862A

公开(公告)日：1994-02-22

申请号：US869171

申请日：1992-04-16

申请人： Takao Saito ,  Hidenori Kumobayashi ,  Shunichi Murahashi

发明人： Takao Saito ,  Hidenori Kumobayashi ,  Shunichi Murahashi

IPC分类号： B01J27/128 ,  B01J31/12 ,  B01J31/30 ,  C07B61/00 ,  C07D205/08 ,  C07F7/18 ,  C07B41/12

CPC分类号： C07F7/186 ,  C07D205/08 ,  C07F7/1892

摘要： A process for preparing a 4-acyloxyazetidinone or a derivative thereof represented by formula (IV): ##STR1## wherein R.sup.1 represents a hydrogen atom, a lower alkyl group, a hydroxyethyl group, or a protected hydroxyethyl group; R.sup.3 represents an alkyl group having from 1 to 10 carbon atoms which may be substituted with a halogen atom, a cyano group, a lower alkoxy group or a phenyl group, or a substituted or unsubstituted phenyl group, provided that the .alpha.-positioned carbon atom of said alkyl group should not have more than two halogen atoms; and R.sup.4 represents a hydrogen atom, a lower alkyl group, or a lower alkoxycarbonyl group, which is useful as an intermediate for penem antibiotics is disclosed, comprising reacting azetidinone or a derivative thereof represented by formula (II): ##STR2## wherein R.sup.1 is as defined above, and R.sup.2 represents a hydrogen atom, a lower alkyl group, a lower alkoxycarbonyl group, or a carboxyl group,with a carboxylic acid represented by formula (III):R.sup.3 COOH (III)wherein R.sup.3 is as defined above,in the presence of (1) a transition metal compound selected from a ruthenium compound, an osmium compound, and a cobalt compound, (2) an aldehyde having 2 or more carbon atoms, provided that the carbon atom at the .alpha.-position thereof should not have two or more halogen atoms, and (3) oxygen. The compound (IV) can be prepared with safety through simple and easy operations.

摘要翻译： 制备由式（IV）表示的4-酰氧基氮杂环丁酮或其衍生物的方法：（*化学结构*）（Ⅳ）其中R1表示氢原子，低级烷基，羟乙基或被保护的羟乙基; R 3表示可以被卤素原子，氰基，低级烷氧基或苯基取代的具有1至10个碳原子的烷基或取代或未取代的苯基，条件是（α）位置 所述烷基的碳原子不应具有多于两个的卤素原子; 并且R4表示可用作penem抗生素中间体的氢原子，低级烷基或低级烷氧基羰基，包括使由式（II）表示的氮杂环丁酮或其衍生物：（*化学结构*） （II）其中R 1如上所定义，并且R 2表示氢原子，低级烷基，低级烷氧基羰基或羧基，与式（III）表示的羧酸：R3COOH（III）其中R3是 如上所述，在（1）选自钌化合物，锇化合物和钴化合物的过渡金属化合物的存在下，（2）具有2个或更多个碳原子的醛，条件是（ α） - 其不应具有两个或更多个卤素原子，和（3）氧。 化合物（IV）可以通过简单和容易的操作安全地制备。

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.

公开(公告)号：US5824822A

公开(公告)日：1998-10-20

申请号：US677226

申请日：1996-07-09

申请人： Takao Saito ,  Akifumi Yoshida ,  Kazuhiko Matsumura ,  Takashi Miura ,  Hidenori Kumobayashi

发明人： Takao Saito ,  Akifumi Yoshida ,  Kazuhiko Matsumura ,  Takashi Miura ,  Hidenori Kumobayashi

IPC分类号： C07D205/08 ,  C07F9/09 ,  C07F9/50 ,  C07F9/655 ,  C07F9/02 ,  C07D205/00

CPC分类号： C07F9/65517 ,  C07D205/08 ,  C07F9/5022 ,  Y02P20/55

摘要： A phosphine-phosphinite compound represented by formula (I): ##STR1## wherein R.sup.1 and R.sup.2, which may be the same or different, each represent a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, and a process for preparing a 4-�(R)-1'-formylethyl!azetidin-2-one derivative using the compound (I). The compound (I), either in combination, or as a complex, with a transition metal compound, is useful as a catalyst for asymmetric hydroformylation and makes it possible to easily synthesize an important intermediate for carbapenem antibiotics or a precursor thereof at high regioselectivity and diastereo-selectivity.

摘要翻译： 由式（I）表示的膦 - 磷化合物：其中R 1和R 2可以相同或不同，各自表示取代或未取代的苯基或取代或未取代的萘基， 用于使用化合物（I）制备4 - [（R）-1'-甲酰乙基]氮杂环丁-2-酮衍生物。 与过渡金属化合物组合或作为络合物的化合物（I）可用作不对称加氢甲酰化的催化剂，并且可以容易地以高区域选择性合成碳青霉烯类抗生素或其前体的重要中间体， 非对映选择性。

公开(公告)号：US5204460A

公开(公告)日：1993-04-20

申请号：US774348

申请日：1991-10-10

申请人： Takao Saito ,  Hidenori Kumobayashi

发明人： Takao Saito ,  Hidenori Kumobayashi

IPC分类号： C07D205/08 ,  C07F7/18

CPC分类号： C07F7/186 ,  C07D205/08

摘要： A simplified process for preparing 4-acetoxyazetidinones of formula (I): ##STR1## wherein Z is a hydrogen atom, a lower alkyl group or a hydroxyethyl group which may or may not be protected is disclosed. According to the invention, azetidinones of formula (II): ##STR2## wherein Z has the same meaning as defined above and Y is a hydrogen atom or a carboxyl group is reacted with acetic acid and an oxidizing agent in the presence of a ruthenium compound represented by the formula [Ru(B).sub.2 (L)].sub.m wherein B is Cl, Br or l, m is a positive integer, and L is 1,5-cyclooctadiene, norbornadiene, cycloheptatriene, cyclooctatetraene or benzene which may or may not have a lower alkyl group as a substituent, as a catalyst.

摘要翻译： 公开了制备式（I）的4-乙酰氧基氮杂环丁酮的简化方法：其中Z是氢原子，低级烷基或可以不被保护的羟乙基。 根据本发明，式（II）的氮杂环丁酮：其中Z具有与上述相同的含义，Y是氢原子或羧基，在乙酸和氧化剂的存在下，与 由式[Ru（B）2（L）] m表示的钌化合物，其中B为Cl，Br或l，m为正整数，L为1,5-环辛二烯，降冰片二烯，环庚三烯，环辛四烯或苯 可以具有或不具有低级烷基作为取代基，作为催化剂。

公开(公告)号：US5081239A

公开(公告)日：1992-01-14

申请号：US442588

申请日：1989-11-29

申请人： Takao Saito ,  Hidenori Kumobayashi

发明人： Takao Saito ,  Hidenori Kumobayashi

IPC分类号： C07D205/08 ,  C07F7/18

CPC分类号： C07F7/186 ,  C07D205/08

摘要： A simplified process for preparing 4-acetoxyazetidinones of formula (I): ##STR1## wherein Z is a hydrogen atom, a lower alkyl group or a hydroxyethyl group which may or may not be protected is disclosed. According to the invention, azetidinones of formula (II): ##STR2## wherein Z has the same meaning as defined above and Y is a hydrogen atom or a carboxyl group is reacted with acetic acid and an oxidizing agent in the presence of a ruthenium compound as a catalyst.

摘要翻译： 公开了制备式（I）的4-乙酰氧基氮杂环丁酮的简化方法：其中Z是氢原子，低级烷基或可以不被保护的羟乙基。 根据本发明，式（II）的氮杂环丁酮：其中Z具有与上述相同的含义，Y是氢原子或羧基，在乙酸和氧化剂的存在下，与 钌化合物作为催化剂。