Affiliation:
1. 1Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan
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.
Subject
General Chemical Engineering,General Chemistry
Reference4 articles.
1. For the effects of a boryl substituent on the ring - closing reaction of vinylallene see;Murakami;Am Chem Soc,2004
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3. and and and refs therein;Rudolf;Org Chem Org Chem Am Chem Soc Tetrahedron Lett,1987
4. For an analogous effect in the ring - opening of oxetene see;Shindo;Am Chem Soc,2002
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