A novel B(C(6)F(5))(3)-catalyzed reduction of alcohols and cleavage of aryl and alkyl ethers with hydrosilanes
The primary alcohols 1a-e and ethers 4a-d were effectively reduced to the corresponding hydrocarbons 2 by HSiEt(3) in the presence of catalytic amounts of B(C(6)F(5))(3). To the best of our knowledge, this is the first example of catalytic use of Lewis acid in the reduction of alcohols and ethers with hydrosilanes. The secondary alkyl ethers 4j,k enabled cleavage and/or reduction under similar reaction conditions to produce either the silyl ethers 3m-n or the corresponding alcohol 5a upon subsequent deprotection with TBAF. It was found that the secondary alcohols 1g-i and tertiary alcohol 1j, as well as the tertiary alkyl ether 4l, did not react with HSiEt(3)/(B(C(6)F(5))(3) reducing reagent at all. The following relative reactivity order of substrates was found: primary >> secondary > tertiary. A plausible mechanism for this nontraditional Lewis acid catalyzed reaction is proposed.
Gevorgyan
V
Department of Chemistry, University of Illinois at Chicago, 845 Taylor Street, Chicago, Illinois 60607-7061, and Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
Rubin
M
Benson
S
Liu
JX
Yamamoto
Y