Rational Design and Development of Low‐Price, Scalable, Shelf‐Stable and Broadly Applicable Electrophilic Sulfonium Ylide‐Based Trifluoromethylating Reagents

Abstract

Main observation and conclusionThe development of two highly reactive electrophilic trifluoromethylating reagents (trifluoromethyl)(4‐nitrophenyl)bis(carbomethoxy)methylide (1g) and (trifluoromethyl)(3‐chlorophenyl)bis(carbomethoxy)methylide (1j) through structure‐activity study was described. Under mild conditions, reagent 1g reacted with β‐ketoesters and silyl enol ethers to give α‐trifluoromethylated‐β‐ketoesters or α‐trifluoromethylated ketones in high yields. In addition, reagent 1g could serve as a trifluoromethyl radical for a variety of trifluoromethylative transformations under visible light irradiation, including radical trifluoromethylation of electron‐rich indoles and pyrroles and sodium aryl sulfinates as well as trifluoromethylative difunctionalization with styrene derivatives. On the other hand, as a complimentary, under reductive coupling conditions, reagent 1j reacted with a variety of (hetero)aryl iodides for the formation of trifluoromethylated (hetero)arenes.