Size‐Programmable Matteson‐Type Annulation: Construction of Spirocycles from Simple Cyclic Ketones

Abstract Despite the recent advancement, Matteson‐type reactions are almost exclusively used to construct linear molecules. Herein we report an iterative boron‐homologation approach to construct various carbocycles from a single precursor. This method utilizes an electron‐withdrawing group (EWG) as a handle to enable intramolecular Matteson‐type couplings, leading to diastereoselective and enantioselective ring formation. An intriguing role of the Lewis acid additive is identified. This approach proves to be general for preparing carbocycles with different ring sizes and multiple stereocenters. The annulation processes are also scalable, and the products can undergo various transformations to provide synthetically valuable structural motifs. In addition, this method can be extended to the preparation of diverse hard‐to‐make spirocyclic compounds from simple cyclic ketones. Moreover, an iterative approach to synthesize double spirocycles is also demonstrated.