Jeffrey J. Patricia

Metal-halogen interchange between t-butyllithium and 1-iodo-5-hexenes provides no evidence for single-electron transfer

Abstract No products attributable to cyclization of 5-hexen-1-yl radicals have been detected in reactions of t -butyllithium with 1-iodo-5-hexenes at −78°C. Such experiments provide no evidence for the intermediacy of free-radicals in the metal—halogen interchange of primary alkyliodides with t -C4H9Li.

Reactions of 1-halo-5-hexenes with alkyllithiums. Evidence for a pronounced halogen effect on the mechanism of the metal—halogen interchange reaction of primary alkyl halides

Abstract Reaction of t -BuLi with 1-halo-5-hexenes and 1-halo-6-methyl-5-heptenes at −78°C has revealed that, whereas 1° alkyl iodides are cleanly converted to alkyllithiums in a non-radical process, the corresponding 1° alkyl bromides undergo interchange at least partially via a radical-mediated, SET pathway.

A search for single-electron transfer (set) mechanisms in the reaction of 1,3-dithianyl- and 1,3-oxathianyllithiums with primary halides

Abstract The reaction of 1, 3-dithianyl-, 2-methyl-1, 3-dithianyl- and oxathianyllithium with 6-halo-1-hexenes affords the products expected from a S N 2 (rather than SET) mechanism.