STEREOCHEMISTRY AT SECONDARY CARBON IN ORGANOMETALLIC INSERTION REACTIONS

Article abstract of DOI:10.1016/S0022-328X(00)93826-9

The stereochemistry of insertion reactions occurring at secondary carbon atoms bound to transition metals has been probed by examination of 13C and 1H spectra of 1,4-disubstituted cyclohexyl systems.The reaction of neat sulfur dioxide with cis and trans -4-methylcyclohexyl (pyridine)-cobaloxime leads to the trans and cis -4-methylcyclohexyl-S-sulfinate cobaloximes respectively, indicating inversion of configuration at the reacting carbon atom.A similar inversion is observed in the reaction of sulfur dioxide with 5-C5H5)>, but the triphenylphosphine-induced insertion of carbon monoxide in acetonitrile proceeds with retention of configuration.