Unusual Solvent Effects in the Wittig Reaction of Some Ketones Indicating Initial One-Electron Transfer

Article abstract of DOI:10.1021/ja00378a035

Investigation of the Wittig reaction of adamantanone, 1, and some other ketones in various solvent systems with alkylidenetriphenylphosphoranes indicates an initial one-electron transfer from the ylide to the carbonyl group.In hydrogen-donor solvents, the hydrogen abstraction from the solvents by the radical ions generated by the one-electron transfer competes considerably with the olefin-forming Wittig reaction, giving unexpected reduction of the carbonyl group.It is shown that such reductions become the major pathway when steric hindrance affects the usual olefin-forming Wittig reaction.