公开(公告)号：US20140194638A1

公开(公告)日：2014-07-10

申请号：US14240918

申请日：2012-07-27

申请人： Qilin Zhou ,  Shoufei Zhu ,  Yanbo Yu ,  Kun Li ,  Lixin Wang

发明人： Qilin Zhou ,  Shoufei Zhu ,  Yanbo Yu ,  Kun Li ,  Lixin Wang

IPC分类号： C07F9/50 ,  C07F15/00

CPC分类号： C07F15/004 ,  B01J31/189 ,  B01J2231/645 ,  B01J2531/827 ,  C07B35/02 ,  C07B53/00 ,  C07B2200/07 ,  C07C51/36 ,  C07F9/5022 ,  C07F9/505 ,  C07F15/0033 ,  C07C53/128 ,  C07C57/30 ,  C07C57/58 ,  C07C59/125 ,  C07C59/13 ,  C07C59/64

摘要： The present invention relates to a spirobenzylamine-phosphine, preparation method therefor and use thereof. The compound has a structure represented by formula (I), wherein n=0 to 3; R1, R2, R3, R4, R5, R6, R7, R8 and R9 having a value as defined in claim 1. Starting from the substituted 7-trifluoromesyloxy-7′-diarylphosphino-1,1′-spiro-dihydroindene, the compound is synthesized in a two-step or three-step reactions. The new spirobenzylamine-phosphine is complexed with an iridium precursor and is subjected to ion exchange, to give an Iridium/spirobenzylamine-phosphine complex comprising various anions. The spiro benzyl amine-phosphine/Iridium complex according to the present invention may be used for catalyzing asymmetry hydrogenation of a variety of alpha-substituted acrylic acids, has high activity and enantio-selectivity, and has a good prospect of industrialization.

摘要翻译： 本发明涉及螺苄胺 - 膦，其制备方法及其用途。 该化合物具有由式（I）表示的结构，其中n = 0至3; R1，R2，R3，R4，R5，R6，R7，R8和R9具有如权利要求1所定义的值。从取代的7-三氟甲氧基-7'-二芳基膦基-1,1'-螺 - 二氢茚基开始，化合物 以两步或三步反应合成。 新的螺苄胺 - 膦与铱前体络合并进行离子交换，得到包含各种阴离子的铱/螺苄胺 - 膦络合物。 根据本发明的螺苄基胺 - 膦/铱络合物可用于催化各种α-取代的丙烯酸的不对称氢化，具有高活性和对映选择性，并且具有良好的工业化前景。

公开(公告)号：US09108995B2

公开(公告)日：2015-08-18

申请号：US14240918

申请日：2012-07-27

申请人： Qilin Zhou ,  Shoufei Zhu ,  Yanbo Yu ,  Kun Li ,  Lixin Wang

发明人： Qilin Zhou ,  Shoufei Zhu ,  Yanbo Yu ,  Kun Li ,  Lixin Wang

IPC分类号： C07F9/50 ,  C07F15/00 ,  C07B35/02 ,  C07B53/00 ,  C07C51/36 ,  B01J31/18

CPC分类号： C07F15/004 ,  B01J31/189 ,  B01J2231/645 ,  B01J2531/827 ,  C07B35/02 ,  C07B53/00 ,  C07B2200/07 ,  C07C51/36 ,  C07F9/5022 ,  C07F9/505 ,  C07F15/0033 ,  C07C53/128 ,  C07C57/30 ,  C07C57/58 ,  C07C59/125 ,  C07C59/13 ,  C07C59/64

摘要： The present invention relates to a spirobenzylamine-phosphine, preparation method therefor and use thereof. The compound has a structure represented by formula (I), wherein n=0 to 3; R1, R2, R3, R4, R5, R6, R7, R8 and R9 having a value as defined in claim 1. Starting from the substituted 7-trifluoromesyloxy-7′-diarylphosphino-1,1′-spiro-dihydroindene, the compound is synthesized in a two-step or three-step reactions. The new spirobenzylamine-phosphine is complexed with an iridium precursor and is subjected to ion exchange, to give an Iridium/spirobenzylamine-phosphine complex comprising various anions. The spiro benzyl amine-phosphine/Iridium complex according to the present invention may be used for catalyzing asymmetry hydrogenation of a variety of alpha-substituted acrylic acids, has high activity and enantio-selectivity, and has a good prospect of industrialization.

摘要翻译： 本发明涉及螺苄胺 - 膦，其制备方法及其用途。 该化合物具有由式（I）表示的结构，其中n = 0至3; R1，R2，R3，R4，R5，R6，R7，R8和R9具有如权利要求1所定义的值。从取代的7-三氟甲氧基-7'-二芳基膦基-1,1'-螺 - 二氢茚基开始，化合物 以两步或三步反应合成。 新的螺苄胺 - 膦与铱前体络合并进行离子交换，得到包含各种阴离子的铱/螺苄胺 - 膦络合物。 根据本发明的螺苄基胺 - 膦/铱络合物可用于催化各种α-取代的丙烯酸的不对称氢化，具有高活性和对映选择性，并且具有良好的工业化前景。

公开(公告)号：US08692018B2

公开(公告)日：2014-04-08

申请号：US12989620

申请日：2009-01-20

申请人： Qilin Zhou ,  Shen Li ,  Shoufei Zhu ,  Canming Zhang ,  Lixin Wang

发明人： Qilin Zhou ,  Shen Li ,  Shoufei Zhu ,  Canming Zhang ,  Lixin Wang

IPC分类号： C07C63/04

CPC分类号： C07F9/653 ,  B01J31/189 ,  B01J31/2295 ,  B01J2231/645 ,  B01J2531/827 ,  C07B53/00 ,  C07B2200/07 ,  C07C51/36 ,  C07D263/12 ,  C07D307/54 ,  C07F15/0033 ,  C07F17/02 ,  C07C57/30 ,  C07C59/64

摘要： The present invention relates to a preparation method of carboxylic acids with optical activity, particularly, publishes that very useful chiral carboxylic acids can be obtained by the asymmetric catalytic hydrogenation of tri-substituted α,β-unsaturated carboxylic acids, with the complexes of the chiral phosphor nitrogen ligands and iridium used as the catalysts which show high activity and enantioselectivity (up to 99.8% ee), thus provides a more efficient method with higher enantioselectivity for asymmetric catalytic hydrogenation of chiral carboxylic acid-like compounds, and has important application value to asymmetric hydrogenation of chiral carboxylic acids.

摘要翻译： 本发明涉及具有光学活性的羧酸的制备方法，特别是公开了通过三取代的α，β-不饱和羧酸的不对称催化氢化得到非常有用的手性羧酸， 手性荧光体氮配体和铱用作显示高活性和对映选择性（高达99.8％ee）的催化剂，从而为手性羧酸样化合物的不对称催化氢化提供了更高的对映选择性的更有效的方法，具有重要的应用价值 对手性羧酸的不对称氢化。

公开(公告)号：US20110092732A1

公开(公告)日：2011-04-21

申请号：US12989620

申请日：2009-01-20

申请人： Qilin Zhou ,  Shen Li ,  Shoufei Zhu ,  Canming Zhang ,  Lixin Wang

发明人： Qilin Zhou ,  Shen Li ,  Shoufei Zhu ,  Canming Zhang ,  Lixin Wang

IPC分类号： C07B55/00

CPC分类号： C07F9/653 ,  B01J31/189 ,  B01J31/2295 ,  B01J2231/645 ,  B01J2531/827 ,  C07B53/00 ,  C07B2200/07 ,  C07C51/36 ,  C07D263/12 ,  C07D307/54 ,  C07F15/0033 ,  C07F17/02 ,  C07C57/30 ,  C07C59/64

摘要： The present invention relates to a preparation method of carboxylic acids with optical activity, particularly, publishes that very useful chiral carboxylic acids can be obtained by the asymmetric catalytic hydrogenation of tri-substituted α,β-unsaturated carboxylic acids, with the complexes of the chiral phosphor nitrogen ligands and iridium used as the catalysts which show high activity and enantioselectivity (up to 99.8% ee), thus provides a more efficient method with higher enantioselectivity for asymmetric catalytic hydrogenation of chiral carboxylic acid-like compounds, and has important application value to asymmetric hydrogenation of chiral carboxylic acids.

摘要翻译： 本发明涉及具有光学活性的羧酸的制备方法，特别是公开了通过三取代的α，β-不饱和羧酸的不对称催化氢化得到非常有用的手性羧酸， 手性荧光体氮配体和铱用作显示高活性和对映选择性（高达99.8％ee）的催化剂，从而为手性羧酸样化合物的不对称催化氢化提供了更高的对映选择性的更有效的方法，具有重要的应用价值 对手性羧酸的不对称氢化。

公开(公告)号：US08450493B2

公开(公告)日：2013-05-28

申请号：US12989610

申请日：2009-01-20

申请人： Qilin Zhou ,  Shoufei Zhu ,  Shen Li ,  Lixin Wang ,  Song Song

发明人： Qilin Zhou ,  Shoufei Zhu ,  Shen Li ,  Lixin Wang ,  Song Song

IPC分类号： C07F15/00 ,  C07F9/653 ,  C07C51/36

CPC分类号： C07F9/653 ,  B01J31/189 ,  B01J2231/645 ,  B01J2531/827 ,  C07B2200/07 ,  C07C51/36 ,  C07F15/0033 ,  C07F15/0046 ,  C07C59/68 ,  C07C57/30

摘要： The present invention belongs to a spiro phosphine-oxazoline and preparation method and application thereof, particularly, publishes a novel spiro phosphine-oxazoline and the preparation method of its iridium complex. The substituted 7-diaryl phosphino-7′-carboxy-1,1′-Lo-dihydro-indene is used as the starting raw material to synthesize the novel spiro phosphine-oxazoline of the present invention through a two-step reaction. The novel spiro phosphine-oxazoline and the iridium precursor are complexed to become a complex, and then through ion exchange, an iridium/phosphine spiro-oxazoline complex with different anions can be obtained. The present invention overcomes the shortcomings of the existing technology. The cheap readily available amino alcohol is used as the raw material to synthesize the novel spiro phosphine-oxazoline, on the fourth position of the oxazoline ring of which there is no substitutent. The iridium complex of this novel spiro phosphine-oxazoline can catalyze the asymmetric hydrogenation of α-substituted acrylic acid, and shows very high activity and enantioselectivity, therefore has a very high research value and an industrialization prospect.

摘要翻译： 本发明属于螺膦 - 恶唑啉及其制备方法和应用，特别是出版了一种新型的辛基膦恶唑啉及其铱络合物的制备方法。 使用取代的7-二芳基膦基-7'-羧基-1,1'-二氢 - 茚作为起始原料，通过两步反应合成本发明的新型螺膦 - 恶唑啉。 新型螺膦 - 恶唑啉和铱前体络合成为络合物，然后通过离子交换，可以获得具有不同阴离子的铱/膦螺恶唑啉络合物。 本发明克服了现有技术的缺点。 在不具有取代基的恶唑啉环的第四位上，使用便宜的氨基醇作为合成新型螺膦 - 恶唑啉的原料。 该新型螺膦 - 恶唑啉的铱络合物可以催化α-取代的丙烯酸的不对称氢化，显示出非常高的活性和对映选择性，具有很高的研究价值和工业化前景。

公开(公告)号：US08962839B2

公开(公告)日：2015-02-24

申请号：US13885051

申请日：2011-11-18

申请人： Qilin Zhou ,  Jianhua Xie ,  Xiaoyan Liu ,  Jianbo Xie ,  Lixin Wang

发明人： Qilin Zhou ,  Jianhua Xie ,  Xiaoyan Liu ,  Jianbo Xie ,  Lixin Wang

IPC分类号： 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分类号： 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

摘要： 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.

摘要翻译： 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

申请人： Qilin Zhou ,  Jianhua Xie ,  Xiaoyan Liu ,  Jianbo Xie ,  Lixin Wang

发明人： Qilin Zhou ,  Jianhua Xie ,  Xiaoyan Liu ,  Jianbo Xie ,  Lixin Wang

IPC分类号： B01J31/24 ,  C07B41/02

CPC分类号： 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

摘要： 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.

摘要翻译： 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：US20110118472A1

公开(公告)日：2011-05-19

申请号：US12989610

申请日：2009-01-20

申请人： Qilin Zhou ,  Shoufej Zhu ,  Shen Li ,  Lixin Wang ,  Song Song

发明人： Qilin Zhou ,  Shoufej Zhu ,  Shen Li ,  Lixin Wang ,  Song Song

IPC分类号： C07F9/653 ,  C07C51/36

CPC分类号： C07F9/653 ,  B01J31/189 ,  B01J2231/645 ,  B01J2531/827 ,  C07B2200/07 ,  C07C51/36 ,  C07F15/0033 ,  C07F15/0046 ,  C07C59/68 ,  C07C57/30

摘要： The present invention belongs to a spiro phosphine-oxazoline and preparation method and application thereof, particularly, publishes a novel spiro phosphine-oxazoline and the preparation method of its iridium complex. The substituted 7-diaryl phosphino-7′-carboxy-1,1′-Lo-dihydro-indene is used as the starting raw material to synthesize the novel spiro phosphine-oxazoline of the present invention through a two-step reaction. The novel spiro phosphine-oxazoline and the iridium precursor are complexed to become a complex, and then through ion exchange, an iridium/phosphine spiro-oxazoline complex with different anions can be obtained. The present invention overcomes the shortcomings of the existing technology. The cheap readily available amino alcohol is used as the raw material to synthesize the novel spiro phosphine-oxazoline, on the fourth position of the oxazoline ring of which there is no substitutent. The iridium complex of this novel spiro phosphine-oxazoline can catalyze the asymmetric hydrogenation of α-substituted acrylic acid, and shows very high activity and enantioselectivity, therefore has a very high research value and an industrialization prospect.

摘要翻译： 本发明属于螺膦 - 恶唑啉及其制备方法和应用，特别是出版了一种新型的辛基膦恶唑啉及其铱络合物的制备方法。 使用取代的7-二芳基膦基-7'-羧基-1,1'-二氢 - 茚作为起始原料，通过两步反应合成本发明的新型螺膦 - 恶唑啉。 新型螺膦 - 恶唑啉和铱前体络合成为络合物，然后通过离子交换，可以获得具有不同阴离子的铱/膦螺恶唑啉络合物。 本发明克服了现有技术的缺点。 在不具有取代基的恶唑啉环的第四位上，使用便宜的氨基醇作为合成新型螺膦 - 恶唑啉的原料。 该新型螺膦 - 恶唑啉的铱络合物可以催化α-取代的丙烯酸的不对称氢化，显示出非常高的活性和对映选择性，具有很高的研究价值和工业化前景。