Redox-Neutral Synthesis of α-Iminonitriles, α-Cyanoenamines, and N-Acyl Derivatives from Amides

Abstract

Although biomimetic or bioinspired synthesis is a widely used and powerful strategy for the efficient synthesis of naturally occurring molecules, prebiomimetic synthesis or prebioinspired organic synthesis has remained unprecedented. Herein, we report the first prebiomimetic synthesis of α-iminonitriles, N-monosubstituted and N,N-disubstituted α-cyanoenamines, and N-acyl derivatives from amides. The method is inspired by the possible prebiotic pathways put forward by Saladino/Di Mauro and Springsteen/Krishnamurthy–Leszczynski/Gu and features triflic anhydride (Tf2O)-mediated redox-neutral cyanation of secondary amides with trimethylsilyl cyanide (TMSCN) under mild conditions.