Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

8-2015

Journal or Book Title

Chemical Science

Volume

6

Issue

12

First Page

6901

Last Page

6907

DOI

10.1039/c5sc02435h

Abstract

ToMMgHB(C6F5)3 (1, ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate) catalyzes the 1,4-hydrosilylation of α,β-unsaturated esters. This magnesium hydridoborate compound is synthesized by the reaction of ToMMgMe, PhSiH3, and B(C6F5)3. Unlike the transient ToMMgH formed from the reaction of ToMMgMe and PhSiH3, the borate adduct 1 persists in solution and in the solid state. Crystallographic characterization reveals tripodal coordination of the HB(C6F5)3 moiety to the six-coordinate magnesium center with a ∠Mg–H–B of 141(3)°. The pathway for formation of 1 is proposed to involve the reaction of ToMMgMe and a PhSiH3/B(C6F5)3 adduct because the other possible intermediates, ToMMgH and ToMMgMeB(C6F5)3, react to give an intractable black solid and ToMMgC6F5, respectively. Under catalytic conditions, silyl ketene acetals are isolated in high yield from the addition of hydrosilanes to α,β-unsaturated esters with 1 as the catalyst.

Comments

This article is from Chemical Science 6 (2015): 6901, doi: 10.1039/c5sc02435h. Posted with permission.

Rights

This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Copyright Owner

Royal Society of Chemisgtry

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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