F- Nucleophilic-Addition-Induced Allylic Alkylation

J Am Chem Soc. 2016 Dec 14;138(49):15869-15872. doi: 10.1021/jacs.6b11205. Epub 2016 Dec 5.

Abstract

Herein we present a novel strategy based on palladium-catalyzed allylic alkylation by taking advantage of the nucleophilic addition of external fluoride onto gem-difluoroalkenes as the initiation step. The merit of this protocol is highly appealing, as it enables a formal allylation of trifluoroethylarene derivatives through the in situ generation of β-trifluorocarbanions, which otherwise are deemed to be problematic in deprotonative allylation. Furthermore, this strategy distinguishes itself by high modularity, operational simplicity, and wide substrate scope with respect to allyl carbonates, giving rise to a broad array of homoallyltrifluoromethane derivatives, which otherwise would not be easily obtained using existing synthetic methods.

Publication types

  • Research Support, Non-U.S. Gov't