Investigation of Thermally Induced α-Deoxysilylation of Organosilylated Hydroxylamine Derivatives as a General Method for Nitrene Production

Article abstract of DOI:10.1021/jo00315a024

A variety of organosilylated hydroxylamine derivatives have been synthesized and studied as possible nitrene generators by thermally induced α-deoxysilylation: GN(OR')SiR3 <*> GN + R'OSiR3, where G = EtO2C, ArCO, ArSO2, Me, H, and Ph2PO.The methods used to assess nitrene formation include trapping product characterization, substitutent variation, kinetic activation parameter measurements, Hammett studies, and solvent effects.While the latter two types of precursors were only briefly investigated because of their marked resistance to fragmentation, the combined data for the remaining compounds are consistent with the intermediacy of a nitrene.The existence of alternative deoxysilylation pathways is discussed in some cases, and for comparison with the nitrogen systems reported herein, kinetic activation parameters for α-deoxysilylation about carbon and silicon have been determined.