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
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
收藏
页码:8247 / 8254
页数:8
相关论文
共 50 条
[21]   α-Arylation of Silyl Enol Ethers via Rhodium(III)-Catalyzed C-H Functionalization [J].
Kou, Xuezhen ;
Kou, Kevin G. M. .
ACS CATALYSIS, 2020, 10 (05) :3103-3109
[22]   Mechanistic insight into B(C6F5)3 catalyzed imine reduction with PhSiH3 under stoichiometric water conditions [J].
He, Yunqing ;
Nie, Wanli ;
Xue, Ying ;
Hu, Qishan .
RSC ADVANCES, 2021, 11 (34) :20961-20969
[23]   New Synthetic Strategies for Structured Silicones Using B(C6F5)3 [J].
Brook, Michael A. ;
Grande, John B. ;
Ganachaud, Francois .
SILICON POLYMERS, 2011, 235 :161-183
[24]   Scope and selectivity of B(C6F5)3-catalyzed reactions of the disilane (Ph2SiH)2 [J].
Lee, Peter T. K. ;
Rosenberg, Lisa .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2016, 809 :86-93
[25]   B(C6F5)3-catalyzed methylation of amines using CO2 as a C1 building block [J].
Yang, Zhenzhen ;
Yu, Bo ;
Zhang, Hongye ;
Zhao, Yanfei ;
Ji, Guipeng ;
Ma, Zhishuang ;
Gao, Xiang ;
Liu, Zhimin .
GREEN CHEMISTRY, 2015, 17 (08) :4189-4193
[26]   B(C6F5)3-Regulated Selectivity of Aryl Alkene Hydrosilylation Catalyzed by a [P,C]-Chelate Cobalt(I) Complex [J].
Li, Xiaomiao ;
Yang, Wenjing ;
Li, Qingshuang ;
Sun, Hongjian ;
Hinz, Alexander ;
Li, Xiaoyan .
INORGANIC CHEMISTRY, 2025, 64 (11) :5661-5671
[27]   Comparative Lewis Acidity in Fluoroarylboranes: B(o-HC6F4)3, B(p-HC6F4)3, and B(C6F5)3 [J].
Morgan, Matthew M. ;
Marwitz, Adam J. V. ;
Piers, Warren E. ;
Parvez, Masood .
ORGANOMETALLICS, 2013, 32 (01) :317-322
[28]   B(C6F5)3 mediated arene hydrogenation/transannulation of para-methoxyanilines [J].
Longobardi, Lauren E. ;
Mahdi, Tayseer ;
Stephan, Douglas W. .
DALTON TRANSACTIONS, 2015, 44 (16) :7114-7117
[29]   Photo Lewis acid generators: photorelease of B(C6F5)3 and applications to catalysis [J].
Khalimon, Andrey Y. ;
Shaw, Bryan K. ;
Marwitz, Adam J. V. ;
Piers, Warren E. ;
Blackwell, James M. ;
Parvez, Masood .
DALTON TRANSACTIONS, 2015, 44 (41) :18196-18206
[30]   A Photo Lewis Acid Generator (PhLAG): Controlled Photorelease of B(C6F5)3 [J].
Khalimon, Andrey Y. ;
Piers, Warren E. ;
Blackwell, James M. ;
Michalak, David J. ;
Parvez, Masood .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (23) :9601-9604