Zhijie Ling, Jianlu Wang, Yang‐Zi Liu, Wei-Ping Deng
A palladium-catalyzed asymmetric [3 + 2] cycloaddition of vinylarylcyclopropanes (VACPs) with photogenerated ketenes is disclosed. This method efficiently constructs tetrahydrofurans featuring a quaternary stereocenter with high yields and excellent enantioselectivity (up to 99% ee). The reaction leverages a visible-light-induced Wolff rearrangement of α-diazoketones and employs a tailored chiral P,S-ligand. The aryl substituent on the VACP is proven crucial for achieving high stereocontrol. The protocol demonstrates broad substrate scope and synthetic utility, providing direct access to valuable tetrahydrofurans.