Catalyst-Controlled Regiodivergent C–H Olefination of Furanyl Carbamates through a Rational Approach

Selective functionalization of heteroarenes remains a central challenge in synthetic organic chemistry, given their widespread presence in natural products and pharmacologically active molecules. Although numerous strategies exist for the olefination of five-membered heteroarenes, few enable precise control over regioselectivity. Herein, we report a DFT-supported, catalyst-controlled C–H olefination of cyclic dienol carbamates that allows regioselective access to either C3- or C5-substituted heteroarenes. This strategy provides a rational and versatile platform for achieving positional selectivity in heteroarene functionalization.