Electrochemical Allylic C(sp<sup>3</sup>)–H Isothiocyanation via [3,3]-Sigmatropic Rearrangement
Xuezhuang Gao, Hui He, Kaili Miao, Lin‐Bao Zhang, Shao‐Fei Ni, Ming Li, Weisi Guo
Abstract
The direct allylic C(sp 3 )–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(sp 3 )–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.
Topics & Concepts
Allylic rearrangementChemistrySigmatropic reactionElectrochemistryMedicinal chemistryStereochemistryCombinatorial chemistryOrganic chemistryElectrodePhysical chemistryCatalysisCatalytic C–H Functionalization MethodsRadical Photochemical ReactionsSulfur-Based Synthesis Techniques