Carbamates: A Directing Group for Selective C-H Amidation and Alkylation under Cp*Co(III) Catalysis.

The selective reactivity of carbamate and thiocarbamate toward alkylation and amidation is reported under stable, high-valent, cost-effective cobalt(III) catalysis. This method reveals the wide possibility of designing a different branch of synthetically challenging yet highly promising asymmetric catalysts based on BINOL and SPINOL scaffolds. Late-stage C-H functionalization of l-tyrosine and estrone was also achieved through this approach. The mechanistic study shows that a base-assisted internal electrophilic substitution mechanism is operative here.