Making Full Use of TMSCF 3 : Deoxygenative Trifluoromethylation/Silylation of Amides.

As one of the most powerful trifluoromethylation reagents, (trifluoromethyl)trimethylsilane (TMSCF 3 ) has been widely used for the synthesis of fluorine-containing molecules. However, to the best of our knowledge, the simultaneous incorporation of both TMS- and CF 3 - groups of this reagent onto the same carbon of the products has not been realized. Herein, we report an unprecedented SmI 2 /Sm promoted deoxygenative difunctionalization of amides with TMSCF 3 , in which both silyl and trifluoromethyl groups are incorporated into the final product, yielding α-silyl-α-trifluoromethyl amines with high efficiency. Notably, the silyl group could be further transformed into other functional groups, providing a new method for the synthesis of α-quaternary α-CF 3 -amines.