Deprotonative Silylation of Aromatic C–H Bonds Mediated by a Combination of Trifluoromethyltrialkylsilane and Fluoride

A method for the deprotonative silylation of aromatic C–H bonds has been developed using trifluoromethyltrimethylsilane (CF<sub>3</sub>SiMe<sub>3</sub>, Ruppert–Prakash reagent) and a catalytic amount of fluoride. In this reaction, CF<sub>3</sub>SiMe<sub>3</sub> is considered to act as a base and a silicon electrophile. This process is highly tolerant to various functional groups on heteroarenes and benzenes. Furthermore, this method can be applied to the synthesis of trimethylsilyl group-containing analogs of TAC-101, which is a bioactive synthetic retinoid with selective affinity for retinoic acid receptor α (RAR-α) binding. We also report further transformations of the silylated products into useful derivatives.