Stereospecific and Chemoselective Copper-Catalyzed Deaminative Silylation of Benzylic Ammonium Triflates

被引：53

作者：

Scharfbier, Jonas ^{[1
]}

Gross, Benjamin M. ^{[1
]}

Oestreich, Martin ^{[1
]}

机构：

[1] Tech Univ Berlin, Inst Chem, Str 17 Juni 115, D-10623 Berlin, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 04期

关键词：

copper; nucleophilic substitution; silanes; stereospecificity; transmetalation; SILICON NUCLEOPHILES; CROSS COUPLINGS; SUBSTITUTION; ACTIVATION; SALTS; HYDROSILYLATION; ELECTROPHILES; SILYLBORANES; BORYLATION; REDUCTION;

D O I：

10.1002/anie.201912490

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A method for the synthesis of benzylsilanes starting from the corresponding ammonium triflates is reported. Silyl boronic esters are employed as silicon pronucleophiles, and the reaction is catalyzed by copper(I) salts. Enantioenriched benzylic ammonium salts react stereospecifically through an S(N)2-type displacement of the ammonium group to afford alpha-chiral silanes with inversion of the configuration. A cyclopropyl-substituted substrate does not undergo ring opening, thus suggesting an ionic reaction mechanism with no benzyl radical intermediate.

引用

页码：1577 / 1580

页数：4

共 46 条

[1] [Anonymous], ANGEW CHEM
[2] [Anonymous], 2019, ANGEW CHEM-GER EDIT
[3] [Anonymous], ANGEW CHEM
[4] C(sp3)-Si Cross-Coupling
Baehr, Susanne
Xue, Weichao
Oestreich, Martin
[J]. ACS CATALYSIS, 2019, 9 (01): : 16 - 24
[5] Nickel-Catalyzed Borylation of Benzylic Ammonium Salts: Stereospecific Synthesis of Enantioenriched Benzylic Boronates
Basch, Corey H.
Cobb, Kelsey M.
Watson, Mary P.
[J]. ORGANIC LETTERS, 2016, 18 (01) : 136 - 139
[6] Iridium-Catalyzed Preparation of Silylboranes by Silane Borylation and Their Use in the Catalytic Borylation of Arenes
Boebel, Timothy A.
Hartwig, John F.
[J]. ORGANOMETALLICS, 2008, 27 (22) : 6013 - 6019
[7] One-pot asymmetric synthesis of tert-butanesulfinyl-protected amines from ketones by the in situ reduction of tert-butanesulfinyl ketimines
Borg, G
Cogan, DA
Ellman, JA
[J]. TETRAHEDRON LETTERS, 1999, 40 (37) : 6709 - 6712
[8] CHIRAL ORGANO-SILICON COMPOUNDS IN SYNTHESIS - HIGHLY ENANTIOSELECTIVE SYNTHESIS OF ARYLCARBINOLS
CHAN, TH
PELLON, P
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (23) : 8737 - 8738
[9] Iron-Catalyzed Highly Enantioselective Hydrosilylation of Unactivated Terminal Alkenes
Cheng, Biao
Liu, Wenbo
Lu, Zhan
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2018, 140 (15) : 5014 - 5017
[10] Highly Enantioselective Cobalt-Catalyzed Hydrosilylation of Alkenes
Cheng, Biao
Lu, Peng
Zhang, Heyi
Cheng, Xinpeng
Lu, Zhan
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (28) : 9439 - 9442

← 1 2 3 4 5 →