Through‐Space 1,4‐Ni/H Shift: Unlocking Migration along Coupling Partners in Olefin Borylcarbofunctionalization

Abstract Olefin migratory functionalization is a well‐established strategy for the selective installation of functional groups at remote C(sp 3 )−H positions along an alkyl chain. However, prior research has predominantly focused on migration along the alkene component. Herein, we describe a conceptually new migratory coupling strategy for the difunctionalization of alkenes, where migration selectively occurs along the C(sp 2 ) coupling partner rather than the alkene component, facilitated by a through‐space 1,4‐Ni/H shift. This approach offers a modular three‐component strategy for the selective and efficient construction of densely functionalized alkyl boronates from readily accessible chemicals. Moreover, by integrating the 1,2‐Ni/H shift with the 1,4‐Ni/H shift, this platform has been expanded to achieve a two‐fold migration along both the alkene components and the coupling partners, facilitating selective borylative remote C(sp 3 )─H/C(sp 2 )─H cross‐coupling.