Atroposelective Construction of Nine‐Membered Carbonate‐Bridged Biaryls

We herein demonstrated an efficient method for the atroposelective construction of nine‐membered carbonate‐bridged biaryls through vinylidene ortho‐quinone methide (VQM) intermediates. Diverse products with desirable pharmacological features were synthesized in satisfying yields and good to excellent enantioselectivities. In subsequent bioassays, several agents showed considerable antiproliferative activity via the mitochondrial‐related apoptosis mechanism. Further transformations produced more structural diversity and may inspire new ideas for developing functional molecules. An efficient method for the atroposelective construction of nine‐membered carbonate‐bridged biaryls was achieved through a ring‐expansion process via vinylidene ortho‐quinone methide (VQM) intermediates. This strategy allows the convenient construction of bridged biaryls with broad functional group tolerance under mild conditions. In bioassay studies, several agents showed considerable antiproliferative activity via the mitochondrial‐related apoptosis mechanism.