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.