Alkenes are fundamental functional groups which feature in various materials and bioactive molecules; however, efficient divergent strategies for their stereodefined synthesis are difficult. In this regard, numerous synthetic methodologies have been developed to construct carbon–carbon bonds with regio‐ and stereoselectivity, enabling the predictable and efficient synthesis of stereodefined alkenes. In fact, an appealing alternative approach for accessing challenging stereodefined alkenes molecular frameworks could involve the sequential selective activation and cross‐coupling of strong bonds instead of conventional C–C bond formation. In this study, we introduce a series of programmed site‐ and stereoselective strategies that capitalizes on the versatile reactivity of readily accessible polymetalloid alkenes (i.e. polyborylated alkenes), through a tandem cross‐coupling reaction, which is catalyzed by an organometallic Rh‐complex to produce complex molecular scaffolds. By merging selective C–B and remote C–H bond functionalization, we achieve the in‐situ generation of polyfunctional C(sp2)‐nucleophilic intermediates. These species can be further modified by selective coupling reactions with various C‐based electrophiles, enabling the formation of C(sp2)–C(sp3) bond for the generation of even more complex molecular architectures using the readily available starting polyborylated‐alkenes. Mechanistic and computational studies have provided insight into the origins of the stereoselectivities and C–H activation via a 1,4‐Rh migration process.

Stereoselective C−B and C−H Bonds Functionalization of PolyBorylated Alkenes