Revised Role of Selectfluor in Homogeneous Au‐Catalyzed Oxidative CO Bond Formations

Abstract

Abstract The pairing of transition metal catalysis with the reagent Selectfluor (F‐TEDA–BF 4 ) has attracted considerable attention due to its utility in myriad CC and Cheteroatom bond‐forming reactions. However, little mechanistic information is available for Selectfluor‐mediated transition metal‐catalyzed reactions and controversy surrounds the precise role of Selectfluor in these processes. We present herein a systematic investigation of homogeneous Au‐catalyzed oxidative CO bond‐forming reactions using density functional theory calculations. Currently, Selectfluor is thought to serve as an external oxidant in Au I /Au III catalysis. However, our investigations suggest that these reactions follow a newly proposed mechanism in which Selectfluor functions as an electrophilic fluorinating reagent involved in a fluorination/defluorination cycle. We have also explored Selectfluor‐mediated gold‐catalyzed homocoupling reactions, which, when cyclopropyl propargylbenzoate is used as a substrate, lead to an unexpected byproduct.