Pd-Catalyzed Enantioselective Annulative Naphthylcarbamoylation of Internal Alkynes for Accessing Axially Chiral Exocyclic Alkenes

Axially chiral alkenes have emerged as a class of increasingly valuable scaffolds and have garnered considerable attention in synthetic chemistry. However, the catalytic asymmetric construction of such skeletons remains a formidable challenge, owing to the severe steric hindrance and inherently low conformational stability of these compounds. Herein, we disclose a palladium-catalyzed enantioselective annulative naphthylcarbamoylation reaction of internal alkynes, which enables the synthesis of tetrasubstituted exocyclic alkenes with axial chirality and exclusive Z-selectivity. By employing readily accessible alkyne-tethered carbamoyl chlorides and naphthylboronic acids as starting materials, this asymmetric catalytic protocol delivers a broad range of rarely reported oxindole-based (Z)-atropisomers with moderate to good yields, as well as remarkable chemo-, regio-, stereo-, and enantioselectivities.