Palladium‐Catalyzed Asymmetric [8+2] Dipolar Cycloadditions of Vinyl Carbamates and Photogenerated Ketenes

: Higher-order cycloadditions, particularly [8+2] cycloadditions, are a straightforward and efficient strategy for constructing significant medium-sized architectures. Typically, configuration-restrained conjugated systems are utilized as 8π-components for higher-order concerted cycloadditions. However, for this reason, 10-membered monocyclic skeletons have never been constructed via the catalytic asymmetric [8+2] cycloaddition with high peri- and stereoselectivity. Here, beyond traditional concerted processes, we accomplish an enantioselective [8+2] dipolar cycloaddition via the merger of visible light activation and asymmetric palladium catalysis. This protocol provides a new route to 10-membered monocyclic architectures bearing chiral quaternary stereocenters with high chemo-, peri-, and enantioselectivity. The success of this strategy relied on the facile in-situ generation of Pd-containing 1,8-dipoles and their enantioselective trapping by ketene dipolarophiles, which were formed in situ via a photo-Wolff rearrangement.