Electrochemical Fluorination of Vinyl Boronates Through Donor-Stabilized Vinyl Carbocation Intermediates

Benjamin Wigman; Woojin Lee; Wenjing Wei; Ken Houk; Hosea Nelson

doi:10.26434/chemrxiv-2021-j5lrx

Catalysis

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Electrochemical Fluorination of Vinyl Boronates Through Donor-Stabilized Vinyl Carbocation Intermediates

Working Paper

Benjamin Wigman University of California, Los Angeles ,
Woojin Lee University of California, Los Angeles ,
Wenjing Wei University of California, Los Angeles ,
Ken Houk University of California, Los Angeles ,
Hosea Nelson California Institute of Technology

Abstract

The electrochemical generation of vinyl carbocations from vinyl boronic esters and boronates is reported. Using easy-to-handle nucleophilic fluoride reagents, these intermediates are trapped to form fully substituted vinyl fluorides. Mech-anistic studies support the formation of dicoordinated car-bocations through sequential single-electron oxidation events. Notably, this electrochemical fluorination features fast reaction times and mild conditions. This transfor-mation provides a complementary method to access vinyl fluorides with simple fluoride salts such as TBAF.