Mechanism and origins of regiochemical control in Rh(III)catalyzed oxidative C−H alkenylation and coupling sequence of unprotected 1‑naphthylamines with α,β-unsaturated esters

The rhodium(III)-catalyzed oxidative C−H alkenylation and coupling sequence of unprotected 1-naphthylamines with α,β-unsaturated esters, which were recently developed by our group, provide an efficient strategy for highly regiocontrolled cyclization and a route to producing biologically important alkylidene-1,2-dihydrobenzo[cd]indole scaffolds. The selectivity of this reaction was studied using density functional theory calculations. A detailed computational study of the reaction mechanism indicated that the regiochemistry of the reaction is controlled by several steps: (i) peri-selective C−H activation, (ii) linear-selective migratory insertion, and (iii) hydrogen-bonding-assisted β-hydride elimination, and the preferred pathway based on calculations is in agreement with the experimentally observed cyclization products.