Selective and Controllable Defluorophosphination and Defluorophosphorylation of Trifluoromethylated Enones: An Auxiliary Function of the Carbonyl Group.

The auxiliary function of a carbonyl group in the tunable defluorophosphination and defluorophosphorylation of trifluoromethylated enones with P(O)-containing compounds was demonstrated. Controlled replacement of one or two fluorine atoms in trifluoromethylated enones while maintaining high chemo- and stereoselectivity was achieved under mild conditions, thus enabling diversity-oriented synthesis of skeletally diverse organophosphorus libraries─( Z )-difluoro-1,3-dien-1-yl phosphinates, (1 Z ,3 E )-4-phosphoryl-4-fluoro-buta-1,3-dien-1-yl phosphinates, and ( E )-4-phosphoryl-4-fluoro-1,3-but-3-en-1-ones─in good yields with excellent functional group tolerance.