Selective C-F Bond Allylation of Trifluoromethylalkenes

Selective C-F bond functionalization of CF3 group represents an appealing strategy for the incorporation of pharmaceutically privileged difluoromethylene moiety. Despite the recent significant advancement attained in the functionalization of Ar-CF3 molecules, prescriptions amenable for alkenyl-CF3 congeners remain sufficiently inadequate. Herein, we report a strategically novel protocol for the C-F bond elaboration of trifluoromethylalkene derivatives. By using readily available allyl metallics as nucleophilic coupling partner, the present reaction enables an expedient construction of structurally diversified CF2-bridged 1,5-dienes. Furthermore, the exquisite selectivity observed in this transformation is revealed to be based on the underlying mechanism that consists of a cascade of nucleophilic S(N)2 ' defluorinative allylation and electronically promoted Cope rearrangement.

Automated summary

This study presents a novel protocol for the C-F bond elaboration of trifluoromethylalkene derivatives, allowing for the expedient construction of structurally diversified CF2-bridged 1,5-dienes with exquisite selectivity based on a cascade of nucleophilic S(N)2 ' defluorinative allylation and electronically promoted Cope rearrangement.