Catalytic asymmetric synthesis of chiral endocyclic allenes remains a challenge in allene chemistry owing to unfavored tension and complex chirality. Here, we present a new relay strategy merging Pd-catalyzed asymmetric [3+2] annulation with enyne-Cope rearrangement, providing a facile route to chiral 9-membered endocyclic allenes with high efficiency and enantioselectivity. Moreover, theoretical calculations and experimental studies were performed to illustrate the critical, but unusual Cope rearrangement that allows for the complete central-to-axial chirality transfer.
Keywords: Annulation; Asymmetric Catalysis; Cope Rearrangement; Endocyclic Allenes; Palladium.
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