Dual Reactivity Mode of Vinyl Ethylene Carbonates with Anilines: A Catalyst-Controlled Chemodivergent Entry to N-Heterocycles and the Observation of Unusual Competing Pathways

A unique catalyst-controlled chemodivergent strategy to access 2-vinyl indolines and indole-2-acetates by overcoming the usual allylic reactivity of vinyl ethylene carbonates (VECs) via a tandem C-H/C-O bond activation sequence is disclosed herein. This methodology provides useful molecular scaffolds by following two distinct pathways in a highly step- and atom-economical manner. The pathway features a challenging beta-hydroxide elimination and in the Rh-catalyzed transformation, we have observed unusual competing pathways such as an oxidative insertion of MeOH into Rh(III) to give a putative Rh(V)-H intermediate. Mechanistic insights unveil a new reactivity mode of vinyl ethylene carbonates and open a new avenue for divergent catalysis. Post synthetic modification of the annulated products add additional advantage to the methodology.