Direct Access to Aryl Bis(trifluoromethyl)carbinols from Aryl Bromides or Fluorosulfates: Palladium‐Catalyzed Carbonylation

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. The more the merrier: Described is the direct synthesis of aryl bis(trifluoromethyl)carbinols from aryl bromides and fluorosulfates with a stoichiometric amount of carbon monoxide and two equivalents of trifluoromethyltrimethylsilane. The method exhibits good yields, broad scope, and good functional‐group tolerance, and is suitable for carbon‐isotope labeling.