Katrine Domino, Cedrick Veryser, Benjamin Wahlquist, Cecilie Gaardbo, Karoline T. Neumann, Kim Daasbjerg, Wim M. De Borggraeve, Troels Skrydstrup

https://doi.org/10.1002/anie.201802647

A palladium‐catalyzed carbonylative approach for the direct conversion of (hetero)aryl bromides into their α,α‐bis(trifluoromethyl)carbinols is described, and it employs only stoichiometric amounts of carbon monoxide and trifluoromethyltrimethylsilane. In addition, aryl fluorosulfates proved highly compatible with these reaction conditions. The method is tolerant of a diverse set of functional groups, and it is adaptable to late‐stage carbon‐isotope labeling.