Palladium-catalyzed enantioselective linear allylic alkylation of vinyl benzoxazinanones: An inner-sphere mechanism

Palladium-catalyzed asymmetric allylic alkylation (AAA) of vinyl benzoxazinanones has become an important strategy for the synthesis chiral nitrogen-containing heterocycle compounds. However, linear-selective products rarely been reported. The simultaneous control regio-, E / Z - and enantioselectivities constitutes a major challenge inhibits advancement this chemistry. Herein, we present palladium-catalyzed AAA with α -thiocyanato ketones, affording various thiocyanates characterized high linear-, stereoselectivities. reaction broad substrate scope can be transformed to useful heterocycles. Experimental computational studies suggest inner-sphere mechanism process, which results from acidic coordination effect nucleophilic substrates palladium catalyst. A unique extremely linear-selectivity, E- selectivity stereoselectivity.