C-C Bond Cleavage in O-Centered Mono- and Dianions Derived from α-Dicarbonyl Compounds

Article abstract of DOI:10.1016/0040-4020(95)00580-2

The reaction of organolithium compounds with oxalyl derivatives and cyclic 1,2-dicarbonyl compounds leads to pinacols or ketones derived from homolytic C-C bond cleavage of the intermediate O,O-centered pinacol dianions depending on the ability of the substituents for the stabilisation of the resulting radical anion.The homolysis is induced by electrostatic repulsion of the negatively charged oxygen atoms.