Selective Monodefluorination and Wittig Functionalization of <i>gem</i>-Difluoromethyl Groups to Generate Monofluoroalkenes

Abstract

Monodefluorination of gem-difluoromethyl groups is achieved using a frustrated Lewis pair (FLP) approach. Triarylphosphines and group 13 Lewis acids were surveyed as FLP components, with the combination of P( o-Tol)₃ and B(C₆F₅)₃ found to provide the best results, although the reaction is feasible with more economical components (PPh₃ and BF₃·OEt₂). The α-fluoroalkylphosphonium products arising from the reaction were of lower activity, in regard to further fluoride abstraction, as compared to difluoride starting materials, leading to highly selective monodefluorination. The activated substrates were subject to Wittig reaction protocols to generate a variety of monofluoroalkenes in moderate to high yields.