公开(公告)号：US09006491B2

公开(公告)日：2015-04-14

申请号：US13383208

申请日：2009-12-21

Applicant: Shengming Ma ,  Bo Lü ,  Chunling Fu

Inventor： Shengming Ma ,  Bo Lü ,  Chunling Fu

IPC: C07F9/50 ,  B01J31/24 ,  C07D307/58 ,  C07F9/54 ,  C07B37/04

CPC classification number: B01J31/2404 ,  B01J2231/4227 ,  B01J2231/4283 ,  B01J2531/824 ,  C07B37/04 ,  C07D307/58 ,  C07F9/5022 ,  C07F9/5442 ,  Y02P20/582

Abstract: The current invention relates to the structure, synthesis of dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine or its tetrafluoroborate, as well as its applications in the palladium catalyzed carbon-chlorine bond activation for Suzuki coupling reactions and carbon-nitrogen bond formation reactions. The dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine or its tetrafluoroborate could coordinate with the palladium catalyst to activate the inert carbon-chlorine bond highly selectively and catalyze Suzuki coupling reaction with arylboronic acid or carbon-nitrogen bond formation reaction with organic amines. The current invention uses only one step to synthesize dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine and its tetrafluoroborate is stable in the air. Compared with known synthetic routes of ligands used in activating carbon-chlorine bonds, the method of current invention is short, easy to operate. Moreover, with this type of ligands, the Suzuki coupling products of optically active chlorolactones and arylboronic acids would maintain their configuration and optical purity.

Abstract translation: 本发明涉及二烷基（2,4,6-或2,6-烷氧基苯基）膦或其四氟硼酸盐的结构，以及其在用于Suzuki偶联反应和碳的钯催化碳 - 氯键活化中的应用 - 氮键形成反应。 二烷基（2,4,6-或2,6-烷氧基苯基）膦或其四氟硼酸盐可以与钯催化剂配位，高度选择性地活化惰性碳 - 氯键，并催化与芳基硼酸或碳 - 氮键形成的Suzuki偶联反应 与有机胺反应。 本发明仅使用一步合成二烷基（2,4,6-或2,6-烷氧基苯基）膦，其四氟硼酸盐在空气中稳定。 与用于活化碳 - 氯键的配体的已知合成路线相比，本发明的方法简单，易于操作。 此外，对于这种配体，光学活性氯内酯和芳基硼酸的Suzuki偶联产物将保持其构型和光学纯度。

公开(公告)号：US20140309422A1

公开(公告)日：2014-10-16

申请号：US14114704

申请日：2012-07-03

Applicant: Shengming Ma ,  Bo Lv ,  Chunling Fu

Inventor： Shengming Ma ,  Bo Lv ,  Chunling Fu

IPC: C07F9/59 ,  C07F9/50

CPC classification number: C07F9/59 ,  B01J31/189 ,  B01J2231/42 ,  B01J2531/824 ,  C07F9/5022

Abstract: The present invention relates to the compound of dialkyl(2-alkoxy-6-aminophenyl)phosphine and the preparation method thereof and the application in the palladium catalyzed coupling reactions of aryl chloride and ketone. The dialkyl(2-alkoxy-6-aminophenyl)phosphine of the present invention could coordinate with the palladium catalyst to highly selectively activate the inert carbon-chlorine bond, and to catalyze direct arylation reaction in the α-position of ketones to produce corresponding coupling compounds. The preparation method of the present invention is a simple one-step method which produces the air-stable dialkyl(2-alkoxy-6-aminophenyl)phosphine. Compared with the synthetic routes of ligands to be used in the activation of carbon-chlorine bonds in the prior arts, the preparation method of the present invention has the advantages of short route and easy operation.

Abstract translation: 本发明涉及二烷基（2-烷氧基-6-氨基苯基）膦的化合物及其制备方法以及在芳基氯和酮的钯催化偶联反应中的应用。 本发明的二烷基（2-烷氧基-6-氨基苯基）膦可以与钯催化剂配位，以高度选择性地活化惰性碳 - 氯键，并催化酮的α-位上的直接芳基化反应产生相应的偶联 化合物。 本发明的制备方法是产生空气稳定的二烷基（2-烷氧基-6-氨基苯基）膦的简单的一步法。 与现有技术中用于活化碳 - 氯键的配体的合成路线相比，本发明的制备方法具有路线短，操作方便的优点。

公开(公告)号：US20120197030A1

公开(公告)日：2012-08-02

申请号：US13383208

申请日：2009-12-21

Applicant: Shengming Ma ,  Bo Lü ,  Chunling Fu

Inventor： Shengming Ma ,  Bo Lü ,  Chunling Fu

IPC: C07D307/33 ,  C07F5/02 ,  C07C211/45 ,  C07F9/02

CPC classification number: B01J31/2404 ,  B01J2231/4227 ,  B01J2231/4283 ,  B01J2531/824 ,  C07B37/04 ,  C07D307/58 ,  C07F9/5022 ,  C07F9/5442 ,  Y02P20/582

Abstract: The current invention relates to the structure, synthesis of dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine or its tetrafluoroborate, as well as its applications in the palladium catalyzed carbon-chlorine bond activation for Suzuki coupling reactions and carbon-nitrogen bond formation reactions. The dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine or its tetrafluoroborate could coordinate with the palladium catalyst to activate the inert carbon-chlorine bond highly selectively and catalyze Suzuki coupling reaction with arylboronic acid or carbon-nitrogen bond formation reaction with organic amines. The current invention uses only one step to synthesize dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine and its tetrafluoroborate is stable in the air. Compared with known synthetic routes of ligands used in activating carbon-chlorine bonds, the method of current invention is short, easy to operate. Moreover, with this type of ligands, the Suzuki coupling products of optically active chlorolactones and arylboronic acids would maintain their configuration and optical purity.

Abstract translation: 本发明涉及二烷基（2,4,6-或2,6-烷氧基苯基）膦或其四氟硼酸盐的结构，以及其在用于Suzuki偶联反应和碳的钯催化碳 - 氯键活化中的应用 - 氮键形成反应。 二烷基（2,4,6-或2,6-烷氧基苯基）膦或其四氟硼酸盐可以与钯催化剂配位，高度选择性地活化惰性碳 - 氯键，并与芳基硼酸或碳 - 氮键形成催化Suzuki偶联反应 与有机胺反应。 本发明仅使用一步合成二烷基（2,4,6-或2,6-烷氧基苯基）膦，其四氟硼酸盐在空气中稳定。 与用于活化碳 - 氯键的配体的已知合成路线相比，本发明的方法简单，易于操作。 此外，对于这种配体，光学活性氯内酯和芳基硼酸的Suzuki偶联产物将保持其构型和光学纯度。

公开(公告)号：US09243011B2

公开(公告)日：2016-01-26

申请号：US14114704

申请日：2012-07-03

Applicant: Shengming Ma ,  Bo Lv ,  Chunling Fu

Inventor： Shengming Ma ,  Bo Lv ,  Chunling Fu

IPC: C07F9/50 ,  C07F9/59 ,  B01J31/18

CPC classification number: C07F9/59 ,  B01J31/189 ,  B01J2231/42 ,  B01J2531/824 ,  C07F9/5022

Abstract: The present invention relates to the compound of dialkyl(2-alkoxy-6-aminophenyl)phosphine and the preparation method thereof and the application in the palladium catalyzed coupling reactions of aryl chloride and ketone. The dialkyl(2-alkoxy-6-aminophenyl)phosphine of the present invention could coordinate with the palladium catalyst to highly selectively activate the inert carbon-chlorine bond, and to catalyze direct arylation reaction in the α-position of ketones to produce corresponding coupling compounds. The preparation method of the present invention is a simple one-step method which produces the air-stable dialkyl(2-alkoxy-6-aminophenyl)phosphine. Compared with the synthetic routes of ligands to be used in the activation of carbon-chlorine bonds in the prior arts, the preparation method of the present invention has the advantages of short route and easy operation.

Abstract translation: 本发明涉及二烷基（2-烷氧基-6-氨基苯基）膦的化合物及其制备方法以及在芳基氯和酮的钯催化偶联反应中的应用。 本发明的二烷基（2-烷氧基-6-氨基苯基）膦可以与钯催化剂配位，以高度选择性地活化惰性碳 - 氯键，并催化酮的α-位上的直接芳基化反应产生相应的偶联 化合物。 本发明的制备方法是产生空气稳定的二烷基（2-烷氧基-6-氨基苯基）膦的简单的一步法。 与现有技术中用于活化碳 - 氯键的配体的合成路线相比，本发明的制备方法具有路线短，操作方便的优点。