Ni‐Catalyzed Linearizable Cyclization/Coupling with Detachable Silicon‐Oxygen Linker: Access to 1,2‐Oxasilolanes, 3‐Hydroxysilanes and 4‐Arylalkanols

We disclose a Ni‐catalyzed cyclization/alkylmetal interception reaction in which products are readily linearized to permit regiodefined alkene dicarbofunctionalization. This method offers a convenient route to access 1,2‐oxasilolane heterocycles, 3‐hydroxysilanes and 4‐arylalkanols with the formation of C(sp 3 )−C(sp 3 ) bonds at primary and secondary alkyl carbon centers. In this reaction, a silicon‐oxygen (Si−O) bond functions as a detachable linker that can be delinked with several hydride, alkyl, aryl and vinyl nucleophiles to create profusely functionalized 3‐hydroxysilanes. A silicon motif in the cyclic C(sp 3 )−Si−O construct in 1,2‐oxasilolane heterocycles can also be selectively deleted by Pd‐catalyzed hydrodesilylation affording Si‐ablated linear alcohol products reminiscent of vicinal ethylene dicarbofunctionalization with C(sp 3 ) and C(sp 2 ) carbon sources.