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Please login or sign up for a free trial to access the full content. Method 14: Reaction of Acetals with Isocyanides

DOI: 10.1055/sos-SD-021-00059

Austin, D. J.; Miller, S. M.Science of Synthesis, (200521104.

Isocyanides react with acetals in the presence of titanium(IV) chloride to provide imidoyl chlorides 68, which can be hydrolyzed directly to the corresponding α-alkoxylated amides 69 in good yields. In order to form the imidoyl chloride it seems likely that an active titanium acetal complex is formed initially and this is then attacked at the highly electrophilic carbon site by the carbon terminus of the isocyanide (Scheme 33). The reaction occurs at low temperature but it is unsuitable for substrates that are reactive to strongly Lewis acidic conditions.[‌50‌]

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