73783-40-1Relevant articles and documents
Evidence for Single Electron Transfer in the Reduction of Organic Halides by Lithium Triethylborohydride
Ashby, E.C.,Wenderoth, Bernd,Pham, Tung N.,Park, Won-Suh
, p. 4505 - 4509 (2007/10/02)
Product studies involving the reduction of cyclizable alkyl iodides and bromides, trapping of intermediate radicals by dicyclohexylphosphine, and direct EPR observation of radicals have been used to detect the occurence of a single electron transfer pathway in the reduction of these halides by lithium triethylborohydride.
Occurrence of Electron Transfer in the Reduction of Organic Halides by LiAlH4 and AlH3
Ashby, E. C.,DePriest, R. N.,Goel, A. B.,Wenderoth, Bernd,Pham, Tung N.
, p. 3545 - 3556 (2007/10/02)
A variety of methods have been utilized to detect the occurrence of a single electron transfer pathway in the reduction of alkyl halides by LiAlH4 and AlH3, i.e., (1) product studies of reduction of cyclizable alkyl halides containing the 5-hexenyl group, (2) trapping of intermediate radicals by dicyclohexylphosphine and other trapping agents, (3) direct EPR observation of the trityl radical in the reduction of trityl bromide, and (4) stereochemical studies of the reduction of secondary halides by lithium aluminum deuteride.The extent of electron transfer was found to be a function of the solvent, the substrate, the leaving group, and the hydride reagent.For alkyl iodides, and to a lesser extent bromides, electron transfer was found to be the major reaction pathway; however, no evidence for electron transfer was found for the corresponding chlorides or tosylates.Reduction of (+)-2-octyl iodide by LiAlD4 was found to be much less stereospecific than the corresponding reduction of bromide, chloride, or tosylate, indicating intermediate radical formation in the reduction of the secondary iodide.
CONCERNING THE REDUCTION OF ALKYL HALIDES BY LiAlH4. EVIDENCE THAT AlH3 PRODUCED IN SITU IS THE ONE ELECTRON TRANSFER AGENT.
Ashby, E. C.,DePriest, R. N.,Pham, T. N.
, p. 2825 - 2828 (2007/10/02)
The reduction of 10 and 20 alkyl iodides by LiAlH4 has been shown to involve a radical intermediate formed by the reaction of the alkyl iodide with the AlH3 and LiI produced in situ in conjunction with LiAlH4 rather than by LiAlH4 alone, as evidenced by cyclized products in the reduction of 6-iodo-1-heptene, by the trapping of the radical and by stereochemical studies of the 2-halooctanes.
