Electrochemical Allylic C(sp³)–H Isothiocyanation via [3,3]-Sigmatropic Rearrangement

The direct allylic C(sp3)–H functionalization provides a straightforward protocol for the synthesis of valuable molecules. We report herein the first chemo- and site-selective method for allylic C(sp3)–H isothiocyanation of various internal alkenes under mild electrochemical conditions. This method exhibits broad functional group tolerance and excellent selectivity and can be applied for late-stage isothiocyanation of bioactive molecules. Combined experimental and computational studies indicate that the reaction proceeds via an unexpected [3,3]-sigmatropic rearrangement.