公开(公告)号：US09440891B2

公开(公告)日：2016-09-13

申请号：US14091466

申请日：2013-11-27

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY

Inventor： Yiyang Liu ,  Brian M. Stoltz ,  Robert H. Grubbs ,  Alexey Fedorov ,  Kelly E. Kim

IPC: C07C1/24 ,  C07C1/207

CPC classification number: C07C1/24 ,  C07C1/2078 ,  C07C2531/24 ,  C07C2531/30 ,  C07C11/02

Abstract: The present invention is directed to methods of forming olefins, especially linear alpha olefins from fatty acids or anhydrides, each method comprising: contacting an amount of precursor carboxylic acid anhydride with a palladium catalyst comprising a bidentate bis-phosphine ligand in a reaction mixture so as to form an olefin in a product with the concomittant formation and removal of CO and water from the reaction mixture, either directly or indirectly, wherein the reaction mixture is maintained with a sub-stoichiometric excess of a sacrificial carboxylic acid anhydride, an organic acid, or both, said sub-stoichiometric excess being relative to the amount of the precursor carboxylic acid anhydride. The precursor carboxylic acid anhydride may be added to the reaction mixture directly or formed in situ by the reaction between at least one precursor carboxylic acid with a stoichiometric amount of the sacrificial acid anhydride.

Abstract translation: 本发明涉及从脂肪酸或酸酐形成烯烃，特别是直链α-烯烃的方法，每种方法包括：将一定量的前体羧酸酐与包含二齿双膦配体的钯催化剂反应在反应混合物中，以便 在直接或间接从反应混合物中伴随形成和除去CO和水的产物中形成烯烃，其中反应混合物用亚化学计量过量的牺牲羧酸酐，有机酸， 或两者，所述亚化学计量过量相对于前体羧酸酐的量。 可以将前体羧酸酐直接加入到反应混合物中或通过至少一种前体羧酸与化学计量的牺牲酸酐之间的反应原位形成。

公开(公告)号：US20220185828A1

公开(公告)日：2022-06-16

申请号：US17688122

申请日：2022-03-07

Applicant: California Institute of Technology

Inventor： Anton Toutov ,  Kerry Betz ,  Alexey Fedorov ,  Brian M. Stoltz ,  Wenbo Liu ,  Robert H. Grubbs

IPC: C07F7/08 ,  C07D209/12

Abstract: The present disclosure describes methods for silylating aromatic derivatives, comprising the use of hydrosilanes and potassium hydroxide.

公开(公告)号：US10919917B2

公开(公告)日：2021-02-16

申请号：US16705408

申请日：2019-12-06

Applicant: California Institute of Technology

Inventor： Anton Toutov ,  Kerry Betz ,  Alexey Fedorov ,  Brian M. Stoltz ,  Wenbo Liu ,  Robert H. Grubbs

IPC: C07F7/08 ,  C07D209/12

Abstract: The present disclosure describes methods for silylating heteroaromatic derivatives, comprising the use of hydrosilanes and potassium hydroxide.

公开(公告)号：US10513531B2

公开(公告)日：2019-12-24

申请号：US16159298

申请日：2018-10-12

Applicant: California Institute Of Technology

Inventor： Anton Toutov ,  Kerry Betz ,  Alexey Fedorov ,  Brian M. Stoltz ,  Wenbo Liu ,  Robert H. Grubbs

IPC: C07F7/08 ,  C07D209/12

Abstract: The present disclosure describes novel silylated heteroaromatic derivatives, including those prepared by methods comprising the use of hydrosilanes and at least one strong base, the definition of strong base now also including hydroxide, especially KOH.

公开(公告)号：US10125153B2

公开(公告)日：2018-11-13

申请号：US15804275

申请日：2017-11-06

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY

Inventor： Anton Toutov ,  Kerry Betz ,  Alexey Fedorov ,  Brian M. Stoltz ,  Wenbo Liu ,  Robert H. Grubbs

IPC: C08G75/00 ,  C07F7/08 ,  C07D209/12

Abstract: The present invention describes chemical systems and methods for silylating N—H bonds of aliphatic amines, said system or method comprising or consisting essentially of a mixture of (a) at least one organosilane and (b) at least one hydroxide, especially KOH, said system being preferably, but not necessarily substantially free of a transition-metal compound, and said methods comprising contacting a quantity of the organic substrate with a mixture of (a) at least one organosilane and (b) at least one strong base, under conditions sufficient to replace an N—H bond with a silyl N—Si bond.

公开(公告)号：US09908840B2

公开(公告)日：2018-03-06

申请号：US14043917

申请日：2013-10-02

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY

Inventor： Robert H. Grubbs ,  Alexey Fedorov ,  Anton Toutov ,  Nicholas A. Swisher

IPC: C07D249/18 ,  C07D213/48 ,  C07D213/74 ,  C07D235/10 ,  C07D239/42 ,  C07D241/20 ,  C07C223/06 ,  C07C309/31 ,  C07C209/28 ,  C07C37/50 ,  C07C1/22 ,  C07C37/055 ,  C07C209/62 ,  C07C319/06 ,  C07F7/08

CPC classification number: C07C209/28 ,  C07B2200/05 ,  C07C1/22 ,  C07C37/055 ,  C07C37/50 ,  C07C209/62 ,  C07C319/06 ,  C07F7/081 ,  C07F7/0814 ,  C07C39/15 ,  C07C15/06 ,  C07C15/16 ,  C07C15/18 ,  C07C15/14 ,  C07C15/04 ,  C07C15/02 ,  C07C15/24 ,  C07C211/48 ,  C07C321/26

Abstract: The present invention describes chemical systems and methods for reducing C—O, C—N, and C—S bonds, said system comprising a mixture of (a) at least one organosilane and (b) at least one strong base, said system being substantially free of a transition-metal compound, and said system optionally comprising at least one molecular hydrogen donor compound, molecular hydrogen, or both.

公开(公告)号：US09809607B2

公开(公告)日：2017-11-07

申请号：US14818417

申请日：2015-08-05

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY

Inventor： Anton Toutov ,  Kerry Betz ,  Alexey Fedorov ,  Brian M. Stoltz ,  Wenbo Liu ,  Robert H. Grubbs

IPC: C08G75/00 ,  C07F7/08 ,  C07D209/12

CPC classification number: C07F7/0801 ,  C07D209/12 ,  C07F7/0827 ,  C07F7/0832

Abstract: The present invention describes chemical systems and methods for silylating aromatic organic substrates, said system or method comprising or consisting essentially of a mixture of (a) at least one organosilane and (b) at least one strong base, the definition of strong base now also including KOH, said system being preferably, but not necessarily substantially free of a transition-metal compound, and said methods comprising contacting a quantity of the organic substrate with a mixture of (a) at least one organosilane and (b) at least one strong base, under conditions sufficient to silylate the aromatic substrate.