Divergent Electrochemical Carboamidation of Cyclic Amines

We
developed an electrochemical carboamidation sequence that affords
either cyclic β-amidoamine products via direct functionalization
or linear hydroxybisamide products via a ring opening pathway. The
reaction pathway was dependent on the nature of the N-acyl activating group, with carbamate groups favoring direct isocyanide
addition to the N-acyliminium ion intermediate and
the benzoyl activating group favoring the ring opening–functionalization
pathway. Both protocols are one-pot reaction sequences, have general
applicability, and lead to peptide-like products of greatly increased
molecular complexity.