Mukaiyama addition of (trimethylsilyl)acetonitrile to dimethyl acetals mediated by trimethylsilyl trifluoromethanesulfonate

作者：Downey C Wade^*; Lee Alice Y K; Goodin John R; Botelho Courtney J; Stith William M

来源：Tetrahedron Letters, 2017, 58(36): 3496-3499.

DOI：10.1016/j.tetlet.2017.07.082

• Silicon Lewis acids
• Lewis acid catalysis
• Acetal reactions
• Silyl nitriles
• Methyl ethers

(Trimethylsilyl)acetonitrile reacts smoothly with dimethyl acetals in the presence of stoichiometric trimethylsilyl trifluoromethanesulfonate (TMSOTf) to yield beta-methoxynitriles. The ideal substrates for this reaction are acetals derived from aromatic aldehydes. Elimination to the corresponding alpha,beta-unsaturatednitriles 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.

• 出版日期2017-9-6