Studies on the Ir-Catalyzed C-H amidation using azidoformates

Abstract

Direct installation of free amino group (-$NH_2$) into carbon skeleton has been considered as a highly desirable method for synthetic chemists. The significance is attributed to their interesting biological and pharmaceutical activities as well as the facile coordination to various metals. Since the direct use of ammonia in the transition metal catalysis is remained unattainable, herein we employed azidoformates as the amino source with an easily removable carbamate protecting group. As the N-N bond of the azidoformate acts as an internal oxidant, the reaction did not require external oxidants as additives. This C-H amidation was applicable to C($sp^2$)-H and C($sp^3$)-H bond functionalizations, thus enabling the formation of corresponding amine products by simple deprotection. A brief mechanistic study and synthetic applications are also presented.