Single Electron Transfer in Reactions of Alkyl Halides with Lithium Thiolates

Article abstract of DOI:10.1021/jo00225a041

Single Electron Transfer (SET) in the reaction of lithium thiolates with trityl halides was studied in detail by (1) isolation and identification of all products, (2) studying the effects of the radical trap, dicyclohexylphosphine (DCPH), on product distribution, and (3) studying the effects of light and the presence of p-dinitrobenzene on the reaction rate.The reaction of lithium thiolates with the cyclizable alkyl iodide probe 2,2-dimethyl-1-iodo-5-hexene was also studied.Reactions carried out in the presence of the radical trap, DCPH, yielded up to 22percent hydrocarbon products, suggesting a significant contribution of a SET pathway.Direct spectroscopic detection of radical intermediates was made for reactions of lithium thiolates with well-known one-electron acceptors, such as diaryl ketones, polynuclear hydrocarbons, trityl halides, and 9-bromofluorene.