The [1,3] sigmatropic rearrangement of vinylcyclobutane to cyclohexene is believed to occur via a diradical transition structure. The cyclopropylcarbinyl (CPC) to homoallylic radical rearrangement has been shown to detect radical intermediates. Spiro[bicyclo[3.2.0]hept-2-ene-6,1'-cyclopropane] (1 ) rearranges to form multiple products, including a CPC rearrangement product. A ten-fold rate enhancement observed for the disappearance of 1  compared to that of its parent structure, bicyclo[3.2.0]hept-2-ene, was attributed to cyclopropyl conjugative stabilization of the diradical intermediate. The current study explores the potential for CPC rearrangements in the homologous system, spiro[bicyclo[4.2.0]oct-2-ene-7,1'-cyclopropane] (2 ), while investigating the rate enhancing effect of cyclopropyl conjugative stabilization.

CPC radical clock as a diradical probe and rate enhancement from cyclopropyl conjugative stabilization in the thermal rearrangement of spiro[bicyclo[4.2.0]oct-2-ene-7,1'-cyclopropane]

247th National Meeting (2014)

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