Revised Role of Selectfluor in Homogeneous Au-Catalyzed Oxidative C-O Bond Formations

The pairing of transition metal catalysis with the reagent Selectfluor (F-TEDA-BF4) 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 AuI/ AuIII 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.