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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Ni-Catalyzed Linearizable Cyclization/Coupling with Detachable Silicon-Oxygen Linker: Access to 1,2-Oxasilolanes,
Margaret G Lakomy1, Majji Shankar1, Ava C Del Rio1
1Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania, 16802, United States.
Abstract:
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.
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