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

Abstract

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, (1Z,3E)-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.

Selective Defluoroalkylation and Hydrodefluorination of Trifluoromethyl Groups Photocatalyzed by Dihydroacridine Derivatives

“…These properties make C–F bonds widely employed in various fields, including pharmaceuticals, − agrochemicals, and materials science . The most commonly used approach for synthesizing organic fluorine compounds involves incorporating a fluorine atom or fluoroalkyl group using fluorinated reagents. − However, the selective functionalization of pre-existing C–F bonds within fluoroalkyl groups shows promise as a more flexible and atomically efficient strategy. − …”

Nickel-catalyzed hydrodefluorination/deuterodefluorination of CF3-alkenes with formic acid

“…Zhang's group 14 reported a copper-catalyzed reductive defluorination of β-CF 3 substituted enones using Grignard reagents. Shen and co-workers reported a series of studies 15 on controllable hydrodefluorination and defluorophosphorylation of β-CF 3 substituted enones with HP(O)Ph 2 . Wu and co-workers 16 reported the directed hydrodefluorination of CF 3 -alkenes via a S N 2′ process using rongalite (H-OCH 2 SO 2 Na) as a masked proton source.…”