Conclusive evidence for an SN2-Si mechanism in the B(C6F5)3-catalyzed hydrosilylation of carbonyl compounds:: Implications for the related hydrogenation

被引：337

作者：

Rendler, Sebastian ^{[1
]}

Oestreich, Martin ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2008年 / 47卷 / 32期

关键词：

hydrosilylation; Lewis acids; nucleophilic substitution; reaction mechanisms; silicon;

D O I：

10.1002/anie.200801675

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Just ask silicon: An experimentally straightforward yet effective Walden-type analysis showcases the usefulness of silanes with a stereogenic silicon center as stereochemical probes. The B(C6F5) 3-catalyzed hydrosilylation and likely the related hydrogenation proceed through linear B-H-Si-O transition states, as verified by flawless inversion of the absolute configuration at silicon (see scheme). (Chemical Equation Presented). © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：5997 / 6000

页数：4

共 66 条

[1]

[Anonymous], 2007, SILICON CHEM

[2]

AUSTIN JD, 1964, J CHEM SOC, P2279

[3] A NEW AND GENERAL-SYNTHESIS OF ALPHA-SILYL CARBONYL-COMPOUNDS BY SI-H INSERTION FROM TRANSITION-METAL CATALYZED-REACTIONS OF DIAZO ESTERS AND DIAZO KETONES [J].

BAGHERI, V ;

DOYLE, MP ;

TAUNTON, J ;

CLAXTON, EE .

JOURNAL OF ORGANIC CHEMISTRY, 1988, 53 (26) :6158-6160

[4] Nucleophilic substitution at silicon (SN2@Si) via a central reaction barrier [J].

Bento, A. Patricia ;

Bickelhaupt, F. Matthias .

JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (06) :2201-2207

[5] B(C6F5)3-catalyzed hydrosilation of imines via silyliminium intermediates [J].

Blackwell, JM ;

Sonmor, ER ;

Scoccitti, T ;

Piers, WE .

ORGANIC LETTERS, 2000, 2 (24) :3921-3923

[6] B(C6F5)3-catalyzed silation of alcohols:: A mild, general method for synthesis of silyl ethers [J].

Blackwell, JM ;

Foster, KL ;

Beck, VH ;

Piers, WE .

JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (13) :4887-4892

[7] SOME MOLECULAR-REARRANGEMENTS OF ORGANOSILICON COMPOUNDS [J].

BROOK, AG .

ACCOUNTS OF CHEMICAL RESEARCH, 1974, 7 (03) :77-84

[8]

Chase P. A., 2007, Angew. Chem., V119

[9] Lewis acid-catalyzed hydrogenation:: B(C6F5)3-mediated reduction of imines and nitriles with H2 [J].

Chase, Preston A. ;

Jurca, Titel ;

Stephan, Douglas W. .

CHEMICAL COMMUNICATIONS, 2008, (14) :1701-1703

[10] Metal-free catalytic hydrogenation [J].

Chase, Preston A. ;

Welch, Gregory C. ;

Jurca, Titel ;

Stephan, Douglas W. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (42) :8050-8053

← 1 2 3 4 5 6 7 →