公开(公告)号：US20090043132A1

公开(公告)日：2009-02-12

申请号：US12113582

申请日：2008-05-01

Applicant: Wolfgang Hell ,  Markus Kegel ,  Helmut Buschmann ,  Felix Spindler ,  Detlef Heller ,  Hans-Joachin Drexler

Inventor： Wolfgang Hell ,  Markus Kegel ,  Helmut Buschmann ,  Felix Spindler ,  Detlef Heller ,  Hans-Joachin Drexler

IPC: C07C211/43

CPC classification number: C07C213/08 ,  B01J31/2409 ,  B01J31/2433 ,  B01J31/2438 ,  B01J31/2457 ,  B01J31/2476 ,  B01J31/249 ,  B01J2231/645 ,  B01J2531/0263 ,  B01J2531/0266 ,  B01J2531/0272 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/827 ,  C07C217/62

Abstract: Compounds of the formula II can be hydrogenated to the corresponding butane derivatives in the presence of homogeneous cataslysts composed of metal salts or complexes containing metals selected from the group consisting of Rh, Ir, and Ru and preferably containing diphosphine ligands, with, in addition, excellent optical yields being achieved when one of R2 and R3 is not a hydrogen atom and the diphosphine ligand is chiral.

Abstract translation: 在由含有选自Rh，Ir和Ru的金属和优选含有二膦配体的金属的金属盐或络合物构成的均匀的催化剂存在下，可将式II化合物氢化为相应的丁烷衍生物，另外， 当R2和R3之一不是氢原子并且二膦配体是手性时，获得了优异的光学收率。

公开(公告)号：US20040167339A1

公开(公告)日：2004-08-26

申请号：US10775803

申请日：2004-02-10

Applicant: The Penn State Research Foundation

Inventor： Xumu Zhang

IPC: C07F009/653

CPC classification number: B01J31/2409 ,  B01J31/1625 ,  B01J31/1658 ,  B01J31/24 ,  B01J31/2414 ,  B01J31/2457 ,  B01J31/249 ,  B01J2231/643 ,  B01J2231/645 ,  B01J2531/80 ,  B01J2531/822 ,  C07B53/00 ,  C07C231/18 ,  C07F9/5027 ,  C07F9/5537 ,  C07F9/572 ,  C07F9/6506 ,  C07F9/65515 ,  C07F9/6552 ,  C07F9/65522 ,  C07F9/6561 ,  C07F9/6596 ,  C07C233/05 ,  C07C233/13 ,  C07C233/18

Abstract: Chiral ligands and transition metal complexes based on such chiral ligands useful in asymmetric catalysis are disclosed. The chiral ligands include (R,S,S,R)-DIOP*. The ruthenium complex reduces enamide to the corresponding amine with up to 99% enantioselectivity. The transition metal complexes of the chiral ligands are useful in asymmetric reactions such as asymmetric hydrogenation, hydride transfer, hydrosilylation, hydroboration, hydrovinylation, hydroformylation, hydrocarboxylation, isomerization, allylic alkylation, cyclopropanation, Diels-Alder reaction, Heck reaction, isomerization, Aldol reaction, Michael addition and epoxidation reactions.

Abstract translation: 公开了基于用于不对称催化的这种手性配体的手性配体和过渡金属配合物。 手性配体包括（R，S，S，R）-DIOP *。 钌络合物将酰胺减少至相应的胺，具有高达99％的对映选择性。 手性配体的过渡金属络合物可用于不对称氢化，氢化物转移，氢化硅烷化，氢化，氢化，加氢甲酰化，加氢羧化，异构化，烯丙基烷基化，环丙烷化，狄尔斯 - 阿尔德反应，Heck反应，异构化，醛醇反应 ，迈克尔加成和环氧化反应。

公开(公告)号：US06576772B1

公开(公告)日：2003-06-10

申请号：US09711635

申请日：2000-11-10

Applicant: Xumu Zhang

Inventor： Xumu Zhang

IPC: C07F950

CPC classification number: B01J31/2409 ,  B01J31/1625 ,  B01J31/1658 ,  B01J31/24 ,  B01J31/2414 ,  B01J31/2457 ,  B01J31/249 ,  B01J2231/643 ,  B01J2231/645 ,  B01J2531/80 ,  B01J2531/822 ,  C07B53/00 ,  C07C231/18 ,  C07F9/5027 ,  C07F9/5537 ,  C07F9/572 ,  C07F9/6506 ,  C07F9/65515 ,  C07F9/6552 ,  C07F9/65522 ,  C07F9/6561 ,  C07F9/6596 ,  C07C233/05 ,  C07C233/13 ,  C07C233/18

Abstract: Chiral ligands and transition metal complexes based on such chiral ligands useful in asymmetric catalysis are disclosed. The chiral ligands include (R,S,S,R)-DIOP*. The ruthenium complex reduces enamide to the corresponding amine with up to 99% enantioselectivity. The transition metal complexes of the chiral ligands are useful in asymmetric reactions such as asymmetric hydrogenation, hydride transfer, hydrosilylation, hydroboration, hydrovinylation, hydroformylation, hydrocarboxylation, isomerization, allylic alkylation, cyclopropanation, Diels-Alder reaction, Heck reaction, isomerization, Aldol reaction, Michael addition and epoxidation reactions.

Abstract translation: 公开了基于用于不对称催化的这种手性配体的手性配体和过渡金属配合物。 手性配体包括（R，S，S，R）-DIOP *。 钌络合物将酰胺减少至相应的胺，具有高达99％的对映选择性。 手性配体的过渡金属络合物可用于不对称氢化，氢化物转移，氢化硅烷化，氢化，氢化，加氢甲酰化，加氢羧化，异构化，烯丙基烷基化，环丙烷化，狄尔斯 - 阿尔德反应，Heck反应，异构化，醛醇反应 ，迈克尔加成和环氧化反应。

公开(公告)号：US20180251428A1

公开(公告)日：2018-09-06

申请号：US15756267

申请日：2016-08-10

Applicant: Merck Patent GmbH

Inventor： Luc EBERHARDT ,  Andreas WAECHTLER ,  David MAILLARD ,  Stefan LEHMANN

IPC: C07D217/14 ,  B01J31/12 ,  C07D401/04 ,  B01J31/24

CPC classification number: C07D217/14 ,  B01J31/122 ,  B01J31/2409 ,  B01J31/2452 ,  B01J31/249 ,  B01J2531/0266 ,  B01J2531/827 ,  C07B53/00 ,  C07D401/04

Abstract: The present invention provides methods of preparing Praziquantel, in particular (R)-Praziquantel and analogues thereof in a stereoselective manner. One method involves asymmetric hydrogenation of the following intermediate compound and subsequent cyclization.

公开(公告)号：US20180141966A1

公开(公告)日：2018-05-24

申请号：US15572160

申请日：2016-01-16

Applicant: Zhejiang Jiuzhou Pharmaceutical Co., Ltd.

Inventor： Qilin ZHOU ,  Jianhua XIE ,  Denghui BAO ,  Lixin WANG

IPC: C07F9/50 ,  C07F9/6553 ,  C07C29/149 ,  C07C29/145 ,  B01J31/24 ,  B01J31/22 ,  B01J31/18 ,  B01J37/04

CPC classification number: C07F9/5022 ,  B01J31/189 ,  B01J31/226 ,  B01J31/249 ,  B01J37/04 ,  B01J2231/643 ,  B01J2531/0241 ,  B01J2531/827 ,  C07B53/00 ,  C07C29/145 ,  C07C29/149 ,  C07C67/31 ,  C07C69/675 ,  C07C69/708 ,  C07C231/12 ,  C07C231/18 ,  C07C235/06 ,  C07C269/06 ,  C07C271/22 ,  C07F9/5054 ,  C07F9/655363 ,  C07F15/0033

Abstract: The present invention relates to a chiral spiro phosphine-nitrogen-sulfur (P—N—S) tridentate ligand, preparation method and application thereof. The P—N—S tridentate ligand is a compound represented by Formula I or Formula II, their racemates, optical isomers, or catalytically acceptable salts thereof. The ligand has a primary structure skeleton characterized as a chiral spiro indan skeleton structure with a thio group. The chiral spiro phosphine-nitrogen-sulfur tridentate ligand can be synthesized by reacting racemic or optical active compound 7-diary/alkyl phosphine-7′-amino-1,1′-spiro-dihydro-indene compound having a spiro-dihydro-indene skeleton as the starting material. The chiral spiro P—N—S tridentate ligand being complex with transition metal salt can be used in an asymmetric catalytic hydrogenation reaction for catalyzing carbonyl compound. In particular, in asymmetric hydrogenation reaction process, being complex with iridium for catalyzing β-alkyl-β-keto ester can obtain a high catalytic activity (a catalyst amount of 0.0002% mol) and high enantioselectivity (up to 99.9% ee) result. So the present invention has a practical value for industrial and commercial production.

公开(公告)号：US09669399B2

公开(公告)日：2017-06-06

申请号：US15164002

申请日：2016-05-25

Applicant: AbbVie Inc.

Inventor： Shashank Shekhar ,  Thaddeus S. Franczyk ,  David M. Barnes ,  Travis B. Dunn ,  Anthony R. Haight ,  Vincent S. Chan

IPC: C07F9/6568 ,  C07C303/40 ,  B01J31/24 ,  C07D209/12 ,  C07D213/76 ,  C07D239/54 ,  C07C253/30 ,  C07C201/10 ,  C07D209/34 ,  C07D265/30 ,  C07C1/30 ,  C07C17/093 ,  C07C41/01 ,  C07C45/71 ,  C07C253/14 ,  C07C273/18 ,  C07C303/36 ,  C07C319/14 ,  C07D209/42 ,  C07D295/033 ,  C07F5/02 ,  C07F9/40 ,  C07C1/32 ,  C07C45/68 ,  C07F1/02 ,  C07F9/50 ,  C07C1/26 ,  C07C17/263 ,  C07C17/361 ,  C07C41/30 ,  C07C45/61 ,  C07F5/04 ,  C07F9/48 ,  C07F9/572 ,  C07F9/6503 ,  C07F9/6558 ,  C07F9/6571 ,  B01J31/18

CPC classification number: B01J31/2423 ,  B01J31/189 ,  B01J31/2419 ,  B01J31/2438 ,  B01J31/2466 ,  B01J31/2485 ,  B01J31/249 ,  B01J2231/4211 ,  B01J2231/4227 ,  B01J2231/4277 ,  B01J2231/4283 ,  B01J2231/4288 ,  B01J2231/4294 ,  B01J2231/44 ,  B01J2531/0205 ,  B01J2531/0266 ,  B01J2531/0288 ,  B01J2531/824 ,  B01J2540/10 ,  B01J2540/40 ,  C07C1/26 ,  C07C1/30 ,  C07C1/321 ,  C07C17/093 ,  C07C17/2635 ,  C07C17/361 ,  C07C41/01 ,  C07C41/30 ,  C07C45/61 ,  C07C45/68 ,  C07C45/71 ,  C07C201/10 ,  C07C253/14 ,  C07C253/30 ,  C07C273/1854 ,  C07C273/1863 ,  C07C303/36 ,  C07C303/40 ,  C07C319/14 ,  C07C2531/24 ,  C07C2531/26 ,  C07D209/12 ,  C07D209/34 ,  C07D209/42 ,  C07D213/76 ,  C07D239/54 ,  C07D265/30 ,  C07D295/033 ,  C07F1/02 ,  C07F5/025 ,  C07F5/04 ,  C07F9/4021 ,  C07F9/4841 ,  C07F9/505 ,  C07F9/5072 ,  C07F9/509 ,  C07F9/572 ,  C07F9/65031 ,  C07F9/65583 ,  C07F9/65683 ,  C07F9/657163 ,  Y02P20/52 ,  C07C275/28 ,  C07C311/08 ,  C07C311/21 ,  C07C311/29 ,  C07C255/10 ,  C07C321/30 ,  C07C205/45 ,  C07C15/06 ,  C07C49/784

Abstract: The disclosure is directed to: (a) phosphacycle ligands; (b) catalyst compositions comprising phosphacycle ligands; and (c) methods of using such phosphacycle ligands and catalyst compositions in bond forming reactions.

公开(公告)号：US08962839B2

公开(公告)日：2015-02-24

申请号：US13885051

申请日：2011-11-18

Applicant: Qilin Zhou ,  Jianhua Xie ,  Xiaoyan Liu ,  Jianbo Xie ,  Lixin Wang

Inventor： Qilin Zhou ,  Jianhua Xie ,  Xiaoyan Liu ,  Jianbo Xie ,  Lixin Wang

IPC: C07F9/06 ,  B01J31/24 ,  B01J31/18 ,  C07B53/00 ,  C07C29/145 ,  C07C41/26 ,  C07C67/31 ,  C07D307/83 ,  C07F9/58 ,  C07F9/60 ,  C07B41/02 ,  C07F15/00

CPC classification number: B01J31/249 ,  B01J31/189 ,  B01J2231/643 ,  B01J2531/827 ,  C07B41/02 ,  C07B53/00 ,  C07B2200/07 ,  C07C29/145 ,  C07C41/26 ,  C07C67/31 ,  C07C2601/14 ,  C07C2602/08 ,  C07C2602/10 ,  C07D307/83 ,  C07F9/58 ,  C07F9/60 ,  C07F15/004 ,  C07C33/18 ,  C07C33/28 ,  C07C69/732 ,  C07C69/675 ,  C07C69/734 ,  C07C31/1355 ,  C07C33/20 ,  C07C35/32 ,  C07C35/36 ,  C07C69/76 ,  C07C33/46 ,  C07C43/23 ,  C07C33/22 ,  C07C33/26

Abstract: The present invention relates to a chiral spiro-pyridylamidophosphine ligand compound, synthesis method therefor and application thereof. The chiral spiro-pyridylamidophosphine compound is a compound having a structure of Formula (I), a racemate or optical isomer thereof, or a catalytically acceptable salt thereof, and is mainly characterized by having a chiral spiro-dihydro-indene skeleton in its structure. The chiral spiro-pyridylamidophosphine compound may be synthesized with optical active 7-diaryl/alkylphosphino-7′-amino-1,1′-spiro-dihydro-indene or substituted 7-diaryl/alkylphosphino-7′-amino-1,1′-spiro-dihydro-indene having a spiro-skeleton as chiral starting material. The chiral spiro-pyridylamidophosphine compound may be used as a chiral ligand in asymmetric hydrogenation of a carbonyl compound catalyzed by iridium, in which the reaction activity is very high, the amount of the catalyst may be 0.0001 mol %, and the enantioselectivity of the reaction is up to 99.9% ee.

Abstract translation: 本发明涉及手性螺 - 吡啶基氨基膦配体化合物，其合成方法及其应用。 手性螺 - 吡啶基氨基膦化合物是具有式（I）结构的化合物，其外消旋物或其旋光异构体或其催化可接受的盐，其主要特征在于在其结构中具有手性螺二氢 - 茚骨架。 手性螺 - 吡啶基氨基膦化合物可以用光学活性7-二芳基/烷基膦基-7'-氨基-1,1'-螺二氢 - 茚或取代的7-二芳基/烷基膦基-7'-氨基-1,1' - 螺 - 二氢 - 茚作为手性起始原料。 手性螺吡啶基氨基膦化合物可以用作由铱催化的羰基化合物的不对称氢化中的手性配体，其中反应活性非常高，催化剂的量可以为0.0001mol％，反应的对映选择性 高达99.9％ee。

公开(公告)号：US20130225822A1

公开(公告)日：2013-08-29

申请号：US13885051

申请日：2011-11-18

Applicant: Qilin Zhou ,  Jianhua Xie ,  Xiaoyan Liu ,  Jianbo Xie ,  Lixin Wang

Inventor： Qilin Zhou ,  Jianhua Xie ,  Xiaoyan Liu ,  Jianbo Xie ,  Lixin Wang

IPC: B01J31/24 ,  C07B41/02

CPC classification number: B01J31/249 ,  B01J31/189 ,  B01J2231/643 ,  B01J2531/827 ,  C07B41/02 ,  C07B53/00 ,  C07B2200/07 ,  C07C29/145 ,  C07C41/26 ,  C07C67/31 ,  C07C2601/14 ,  C07C2602/08 ,  C07C2602/10 ,  C07D307/83 ,  C07F9/58 ,  C07F9/60 ,  C07F15/004 ,  C07C33/18 ,  C07C33/28 ,  C07C69/732 ,  C07C69/675 ,  C07C69/734 ,  C07C31/1355 ,  C07C33/20 ,  C07C35/32 ,  C07C35/36 ,  C07C69/76 ,  C07C33/46 ,  C07C43/23 ,  C07C33/22 ,  C07C33/26

Abstract: The present invention relates to a chiral spiro-pyridylamidophosphine ligand compound, synthesis method therefor and application thereof. The chiral spiro-pyridylamidophosphine compound is a compound having a structure of Formula (I), a racemate or optical isomer thereof, or a catalytically acceptable salt thereof, and is mainly characterized by having a chiral spiro-dihydro-indene skeleton in its structure. The chiral spiro-pyridylamidophosphine compound may be synthesized with optical active 7-diaryl/alkylphosphino-7′-amino-1,1′-spiro-dihydro-indene or substituted 7-diaryl/alkylphosphino-7′-amino-1,1′-spiro-dihydro-indene having a spiro-skeleton as chiral starting material. The chiral spiro-pyridylamidophosphine compound may be used as a chiral ligand in asymmetric hydrogenation of a carbonyl compound catalyzed by iridium, in which the reaction activity is very high, the amount of the catalyst may be 0.0001 mol %, and the enantioselectivity of the reaction is up to 99.9% ee.

Abstract translation: 本发明涉及手性螺 - 吡啶基氨基膦配体化合物，其合成方法及其应用。 手性螺 - 吡啶基氨基膦化合物是具有式（I）结构的化合物，其外消旋物或其旋光异构体或其催化可接受的盐，其主要特征在于在其结构中具有手性螺二氢 - 茚骨架。 手性螺 - 吡啶基氨基膦化合物可以用光学活性7-二芳基/烷基膦基-7'-氨基-1,1'-螺二氢 - 茚或取代的7-二芳基/烷基膦基-7'-氨基-1,1' - 螺 - 二氢 - 茚作为手性起始原料。 手性螺吡啶基氨基膦化合物可以用作由铱催化的羰基化合物的不对称氢化中的手性配体，其中反应活性非常高，催化剂的量可以为0.0001mol％，反应的对映选择性 高达99.9％ee。

公开(公告)号：US06969694B2

公开(公告)日：2005-11-29

申请号：US10775803

申请日：2004-02-10

Applicant: Xumu Zhang

Inventor： Xumu Zhang

IPC: B01J31/24 ,  C07B53/00 ,  C07C231/18 ,  C07C233/05 ,  C07C233/13 ,  C07C233/18 ,  C07F9/50 ,  C07F9/553 ,  C07F9/572 ,  C07F9/6506 ,  C07F9/655 ,  C07F9/6561 ,  C07F9/6596 ,  B01J31/00

CPC classification number: B01J31/2409 ,  B01J31/1625 ,  B01J31/1658 ,  B01J31/24 ,  B01J31/2414 ,  B01J31/2457 ,  B01J31/249 ,  B01J2231/643 ,  B01J2231/645 ,  B01J2531/80 ,  B01J2531/822 ,  C07B53/00 ,  C07C231/18 ,  C07F9/5027 ,  C07F9/5537 ,  C07F9/572 ,  C07F9/6506 ,  C07F9/65515 ,  C07F9/6552 ,  C07F9/65522 ,  C07F9/6561 ,  C07F9/6596 ,  C07C233/05 ,  C07C233/13 ,  C07C233/18

Abstract: Chiral ligands and transition metal complexes based on such chiral ligands useful in asymmetric catalysis are disclosed. The chiral ligands include (R,S,S,R)-DIOP*. The ruthenium complex reduces enamide to the corresponding amine with up to 99% enantioselectivity. The transition metal complexes of the chiral ligands are useful in asymmetric reactions such as asymmetric hydrogenation, hydride transfer, hydrosilylation, hydroboration, hydrovinylation, hydroformylation, hydrocarboxylation, isomerization, allylic alkylation, cyclopropanation, Diels-Alder reaction, Heck reaction, isomerization, Aldol reaction, Michael addition and epoxidation reactions.The chiral ligands are of the formula the identittes of the R, R′ and Y groups are defined herein.

Abstract translation: 公开了基于用于不对称催化的这种手性配体的手性配体和过渡金属配合物。 手性配体包括（R，S，S，R）-DIOP *。 钌络合物将酰胺减少至相应的胺，具有高达99％的对映选择性。 手性配体的过渡金属络合物可用于不对称氢化，氢化物转移，氢化硅烷化，氢化，氢化，加氢甲酰化，加氢羧化，异构化，烯丙基烷基化，环丙烷化，狄尔斯 - 阿尔德反应，Heck反应，异构化，醛醇反应 ，迈克尔加成和环氧化反应。 手性配体具有下式：R，R'和Y基团的定义如本文所定义。

公开(公告)号：US06278024B1

公开(公告)日：2001-08-21

申请号：US09524787

申请日：2000-03-13

Applicant: Xumu Zhang

Inventor： Xumu Zhang

IPC: C07F950

CPC classification number: C07B53/00 ,  B01J31/0244 ,  B01J31/185 ,  B01J31/1875 ,  B01J31/2414 ,  B01J31/2457 ,  B01J31/2466 ,  B01J31/2476 ,  B01J31/248 ,  B01J31/2485 ,  B01J31/249 ,  B01J31/26 ,  B01J2231/32 ,  B01J2231/643 ,  B01J2231/645 ,  B01J2531/0205 ,  B01J2531/80 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/824 ,  B01J2531/827 ,  B01J2531/828 ,  B01J2531/842 ,  C07B2200/07 ,  C07C29/145 ,  C07C41/26 ,  C07C45/505 ,  C07C231/18 ,  C07F9/46 ,  C07F9/5027 ,  C07F9/572 ,  C07F9/59 ,  C07F9/6561 ,  C07F9/65683 ,  C07F9/65746 ,  C07F15/004 ,  C07F15/0053 ,  C07F15/0066 ,  C07F15/008 ,  C07F15/045 ,  C07C33/22 ,  C07C33/20 ,  C07C43/23 ,  C07C33/18 ,  C07C31/125 ,  C07C31/12 ,  C07C31/1355

Abstract: This invention is to develop novel transition metal catalysts for the practical synthesis of important chiral molecules. The invention emphasizes asymmetric catalysis based on chiral bidentate phosphine ligands with cyclic ring structures which could be used to restrict conformational flexibility of the ligands and thus the efficiency of chiral transfer can be enhanced through the ligand rigidity

Abstract translation: 本发明是开发用于实际合成重要手性分子的新型过渡金属催化剂。 本发明强调了基于具有环状结构的手性二齿膦配体的不对称催化作用，其可用于限制配体的构象柔性，从而可以通过配体刚性增强手性转移的效率