(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.
© 2017 Elsevier Ltd.
The definitive version is available at: https://www.sciencedirect.com/science/article/pii/S0040403917309462.
Wade-Downey, C., Alice Y.-K. Lee, John R. Goodin, Courtney J. Botelho, and William M. Stith. "Mukaiyama addition of (trimethylsilyl)acetonitrile to dimethyl acetals mediated by trimethylsilyl trifluoromethanesulfonate." Tetrahedron Letters 58, no. 36 (September 2017): 3496-3499. doi:10.1016/j.tetlet.2017.07.082.
Downey, C. Wade; Lee, Alice Y.-K.; Goodin, John R.; Botelho, Courtney J.; and Stith, William M., "Mukaiyama addition of (trimethylsilyl) acetonitrile to dimethyl acetals mediated by trimethylsilyl trifluoromethanesulfonate" (2017). Chemistry Faculty Publications. 50.