Enantioselective\nExcited-State Nazarov Reaction: A\nRelay Strategy of Electrocyclization and Parallel Kinetic Resolution

We report herein the enantioselective\nphotoinduced Nazarov\nreaction\nusing a relay strategy of an electrocyclization, followed by parallel\nkinetic resolution (PKR). No enantioselectivity was observed during\nelectrocyclization due to weak coordination between chiral ligands\nand the substrate’s carbonyl group. However, PKR was successfully\nachieved in the deprotonation step with a bifunctional chiral thiourea\nligand. Regioselective deprotonation, controlled by the chiral <i>N,N</i>-dimethyl amine motif, produced <i>cis</i>-6,5,6-fused\ntricyclic stereoisomers with high ee and yields.