Selective Monodefluorination and Wittig Functionalization of gem-Difluoromethyl Groups to Generate Monofluoroalkenes

• Published in: Journal of the American Chemical Society Vol. 140; no. 34; pp. 10682 - 10686
• Main Authors: Mandal, Dipendu, Gupta, Richa, Young, Rowan D
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 29-08-2018
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.8b06770

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.