THE REACTION OF CARBANIONS WITH TERT-BUTYL RADICALS

Article abstract of DOI:10.1016/S0040-4020(01)97189-3

The S_RNl free radical chain reaction of Me3CHgCl with nitronate <^-O2N=C(R₁)(R₂)> and phenone enolate -)=C(R₁)(R₂)> anions yields the C-alkylation products 1)(R₂)NO2, PhCOC(R₁)(R₂)CMe3>.Competitive reactions between pairs of anions demonstrate that as the basicity of the anion increases the reactivity toward Me3C<*>at first increases and then decreases.An inverted reactivity order is also observed with phenylacetonitrile anions.In early transition state reactions, the nucleophilic character of the tert-butyl radical apparently controls the reactivity by virtue of a transition state involving transfer of the electron from radical to the LUMO of the resonance stabilized anion.