In:
Pure and Applied Chemistry, Walter de Gruyter GmbH, Vol. 78, No. 2 ( 2006-01-01), p. 415-423
Abstract:
The silyl substituent of 3-silylcyclobutene prefers inward rotation rather than outward rotation during a thermal ring-opening reaction, giving the Z -isomer predominantly. This intriguing behavior was explained by assuming electron-accepting interactions between the low-lying σ*-orbital of the silicon-carbon linkage and the highest occupied molecular orbital (HOMO) of the opening cyclobutene system, which are possible only in the inward transition state. On the basis of this finding, a novel method for the stereoselective synthesis of functionalized 1,3-butadiene derivatives from cyclobutenones was developed. Boryl substituents exhibit even stronger preference for inward rotation than silyl substituents as a result of electron delocalization from the cyclobutene HOMO into the vacant p-orbital of boron at the inward transition state.
Type of Medium:
Online Resource
ISSN:
1365-3075
,
0033-4545
DOI:
10.1351/pac200678020415
Language:
English
Publisher:
Walter de Gruyter GmbH
Publication Date:
2006
detail.hit.zdb_id:
2022101-0
