Published Online: 15 SEP 2010
Copyright © 2010 John Wiley & Sons, Inc. All rights reserved.
Comprehensive Organic Name Reactions and Reagents
How to Cite
2010. Vinylcyclopropane Rearrangement. Comprehensive Organic Name Reactions and Reagents. 2880–2887.
- Published Online: 15 SEP 2010
This reaction is a thermal [1,3]-sigmatropic carbon shift of vinylcyclopropanes to cyclopentenes and is generally known as a vinylcyclopropane rearrangement, or vinylcyclopropane-cyclopentene rearrangement. The study finds that this rearrangement can undergo three types of reactions. The experimental evidence shows that the vinylcyclopropane rearrangement to cyclopentene is the dominating reaction because of the heat of formation of cyclopentene is lower than that of vinylcyclopropane, and the activation energy for the vinylcyclopropane rearrangement is lower than that of epimerization. In addition, an extra group on the cyclopropane ring can further lower the activation energy for the vinylcyclopropane rearrangement and an additional group on the vinyl moiety and at the cis-position will decrease the reaction rate. Furthermore, the silyl group enhances the reaction rate and stereoselectivity, owing to the hyperconjugation between the carbon-silyl bond and the vicinal cyclopropane ring orbital. This reaction has very broad application in organic synthesis.