Pan Pan, Shihao Li, J Chen, J F Sun, Yinjie Li, Zitong Rong, Nai‐Dong Chen
Herein, a trifluoroacetylation difunctionalization reaction of electron-deficient alkenes has been developed via a visible-light catalytic strategy. Initially, the trifluoroacetylation allylation of alkenes was realized by synergistic photoredox and palladium catalysis. Mechanistic investigations revealed that this transformation proceeds sequentially through radical addition, reduction, and substitution processes. Furthermore, trifluoroacetylation amination of alkenes was further achieved via an energy-transfer pathway. Both protocols feature mild reaction conditions, broad substrate scope, and simple operation, providing a convenient difunctionalization strategy for the synthesis of trifluoroacetyl building blocks.