Significant synthetic challenges remain for the asymmetric synthesis of tertiary α-fluoro ketones, which are potentially useful molecules for the development of drugs, agrochemicals, and functional materials. Herein, we describe the development of a method for the catalytic enantioselective synthesis of tertiary α-fluoro ketones via the Tsuji−Trost reaction of racemic acyclic αfluorinated ketones. Enantioenriched acyclic α-cabonyl tertiary fluorides can be produced with the aid of a palladium/phosphinooxazoline catalyst.

CF3-containing esters smoothly reacted with electron-deficient alkenes in the presence of a phosphine (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) organocatalyst at room temperature in an aerobic atmosphere. These Michael reactions efficiently provided products with a CF3 quaternary carbon center.

Organocatalytic Reactions of -Trifluoromethylated Esters with Terminal Alkenes at Room Temperature. -The title reaction proceeds in the presence of a phosphine organocatalyst in an aerobic atmosphere. These Michael reactions efficiently provide products with a CF 3-substituted quaternary carbon center. -(WANG, Q.; HUAN, F.; SHEN, H.; XIAO, J.-C.; GAO, M.; YANG*, X.; MURAHASHI, S.-I.; CHEN, Q.-Y.; GUO, Y.; J. Org. Chem. 78 (2013) 24, 12525-12531, http://dx.