Synthesis of Bridged and Fused Tetracycles via Rhodium‐Catalyzed C−H Allylation/Cycloaddition of Azomethine Imines with MBH Adducts and Allyl Acetates

Abstract A rhodium‐catalyzed cascade C−H allylation combined with exo ‐ and endo ‐type [3+2] dipolar cycloaddition of aryl azomethine imines with Morita‐Baylis‐Hillman (MBH) adducts and allyl acetates is described. This process, which is operationally simple and proceeds efficiently in air and moisture under neat conditions, facilitates diverse bridged and fused tetracycles as single diastereomers. The reaction showcases a broad substrate scope and good functional group compatibility. Furthermore, its practicality is further demonstrated through successful scale‐up and synthetic applications.