B(C6F5)3 catalyzed hydrosilation of enones and silyl enol ethers

被引：146

作者：

Blackwell, JM ^{[1
]}

Morrison, DJ ^{[1
]}

Piers, WE ^{[1
]}

机构：

[1] Univ Calgary, Dept Chem, Calgary, AB T2N 1N4, Canada

来源：

TETRAHEDRON | 2002年 / 58卷 / 41期

基金：

加拿大自然科学与工程研究理事会;

关键词：

Lewis acid catalysis; hydrosilation; enones; silylenol ethers; tris-(pentafluorophenyl)borane;

D O I：

10.1016/S0040-4020(02)00974-2

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The 1,4 hydrosilation of a variety of simple alpha,beta-unsaturated enones as catalyzed by B(C6F5)(3) (1-2%) is described. For substrates with no steric hindrance near the beta-carbon, 1,4 addition of silane is very clean; in other instances, 1,2 hydrosilation is competitive. The reaction is facile with five commercially available silane reagents. For two examples, a novel hydrosilation of the resulting silylenol ethers was also observed. The net trans stereochemistry of H-Si addition to the silylenol ether C=C bond was established and points to a stepwise mechanism for this reaction. This was supported by the observation and full spectroscopic characterization of a silylcarboxonium ion intermediate with an [HB(C6F5)(3)](-) counteranion in the hydrosilation of the silylenol ether derived from 4,4-dimethyl-2-cyclohexen-1-one and PhMe2SiH. (C) 2002 Elsevier Science Ltd. All rights reserved.

引用

页码：8247 / 8254

页数：8

共 50 条

[31] B(C6F5)3-Catalyzed transfer 1,4-hydrostannylation of α,β-unsaturated carbonyls using iPr-tricarbastannatrane [J].

Fillion, Eric ;

Kavoosi, Azadeh ;

Nguyen, Kevin ;

Ieritano, Christian .

CHEMICAL COMMUNICATIONS, 2016, 52 (87) :12813-12816

[32] A self-hydrosilylation of phosphanylhydrosilylalkynes promoted by B(C6F5)3? An experimental and mechanistic study [J].

Huang, Yanting ;

Wang, Xiaoping ;

Li, Yan ;

Yang, Ming-Chung ;

Su, Ming-Der ;

Zhu, Hongping .

CHEMICAL COMMUNICATIONS, 2019, 55 (10) :1494-1497

[33] Borohydrides from Organic Hydrides: Reactions of Hantzsch's Esters with B(C6F5)3 [J].

Webb, Jonathan D. ;

Laberge, Veronique S. ;

Geier, Stephen J. ;

Stephan, Douglas W. ;

Crudden, Cathleen M. .

CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (16) :4895-4902

[34] Mechanism Insights into the Iridium(III)- and B(C6F5)3-Catalyzed Reduction of CO2 to the Formaldehyde Level with Tertiary Silanes [J].

Guzman, Jefferson ;

Urriolabeitia, Asier ;

Padilla, Marina ;

Garcia-Orduna, Pilar ;

Polo, Victor ;

Fernandez-Alvarez, Francisco J. .

INORGANIC CHEMISTRY, 2022, 61 (50) :20216-20221

[35] Activation of Alkynes with B(C6F5)3 - Boron Allylation Reagents Derived from Propargyl Esters [J].

Hansmann, Max M. ;

Melen, Rebecca L. ;

Rominger, Frank ;

Hashmi, A. Stephen K. ;

Stephan, Douglas W. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (02) :777-782

[36] B(C6F5)3: Catalyst or Initiator? Insights from Computational Studies into Surrogate Silicon Chemistry [J].

Banerjee, Subhrashis ;

Vanka, Kumar .

ACS CATALYSIS, 2018, 8 (07) :6163-6176

[37] B(C6F5)3-Catalyzed Transfer Hydrogenation of Imines and Related Heteroarenes Using Cyclohexa-1,4-dienes as a Dihydrogen Source [J].

Chatterjee, Indranil ;

Oestreich, Martin .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (06) :1965-1968

[38] B(C6F5)3-Catalyzed Reduction of Ketones and Imines Using Silicon-Stereogenic Silanes: Stereoinduction by Single-Point Binding [J].

Hog, Daniel T. ;

Oestreich, Martin .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2009, 2009 (29) :5047-5056

[39] B(C6F5)3-Promoted Tandem Silylation and Intramolecular Hydrosilylation: Diastereoselective Synthesis of Oxasilinanes and Oxasilepanes [J].

Shchepin, Roman ;

Xu, Chunping ;

Dussault, Patrick .

ORGANIC LETTERS, 2010, 12 (21) :4772-4775

[40] Quantum Chemical Study of the Reaction of 3-(Trimethylsilyl)cyclohexa-1,4-dienes with B(C6F5)3 [J].

Sakata, Ken ;

Fujimoto, Hiroshi .

ORGANOMETALLICS, 2015, 34 (01) :236-241

← 1 2 3 4 5 →