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

J Am Chem Soc

State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.

Published: July 2024

As one of the most powerful trifluoromethylation reagents, (trifluoromethyl)trimethylsilane (TMSCF) 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- groups of this reagent onto the same carbon of the products has not been realized. Herein, we report an unprecedented SmI/Sm promoted deoxygenative difunctionalization of amides with TMSCF, 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-amines.

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http://dx.doi.org/10.1021/jacs.4c04760DOI Listing

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