Kinetic data and product distributions that have been obtained for a variety of vinylcyclobutane derivatives provide evidence for a stepwise mechanism involving a diradical intermediate in [1,3] sigmatropic rearrangements. This project involves the use of the cyclopropyl methyl carbinyl (CPC) radical clock reaction as a probe for the presence of a diradical in the thermal reactions of spiro[bicyclo[4.2.0]oct-2-ene-7,1'-cyclopropane]. Previous studies by our group have indicated CPC rearrangement as a minor exit channel in the thermal reactions of spiro[bicyclo[3.2.0]hept-2-ene-6,1'-cyclopropane], suggesting that this is a viable diradical probe in the present context. We hypothesize that that the modest increase in the distance between the migrating carbon and its destination that results from the addition of an extra carbon will lead to the formation of a longer-lived diradical than in the spiro[3.2.0] system, allowing the CPC reaction to compete more effectively and contribute to the product distribution to a greater extent.

CPC radical clock reaction as a diradical probe in the thermal reactions of spiro[bicyclo[4.2.0]oct-2-ene-7,1'-cyclopropane]

243rd National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.