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Mukaiyama Addition Of (Trimethylsilyl) Acetonitrile To Dimethyl Acetals Mediated By Trimethylsilyl Trifluoromethanesulfonate, C. Wade Downey, Alice Y.-K. Lee, John R. Goodin, Courtney J. Botelho, William M. Stith

Chemistry Faculty Publications

(Trimethylsilyl) acetonitrile reacts smoothly with dimethyl acetals in the presence of stoichiometric trimethylsilyl trifluoromethanesulfonate (TMSOTf) to yield β-methoxynitriles. The ideal substrates for this reaction are acetals derived from aromatic aldehydes. Elimination to the corresponding α,β-unsaturated nitriles is observed as the major product in the case of electron-rich acetals. A mechanistic hypothesis that includes isomerization of the silylnitrile to a nucleophilic N-silyl ketene imine is presented.