Unexpected Vinylcyclopropane Rearrangement: New Strategies toward Skipped Dienes Using Sulfonium Ylides

Vinylcyclopropanes are key intermediates in organic chemistry which undergo several important rearrangements. Herein, we report on an unexpected rearrangement of vinylcyclopropane into skipped diene proceeding at room temperature and with high selectivity. Deuteration experiments indicate that the mechanism of this rearrangement involves regioselective ring‐opening of the cyclopropane ring followed by 1,2‐migration of an aryl group. Based on this transformation, two complementary strategies toward skipped dienes bearing an aryl group on the central center were developed using sulfonium ylides.