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(sp3)‐C(sp3) 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(sp3)‐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(sp3) and C(sp2) carbon sources.