3050-61-1Relevant academic research and scientific papers
Evidence for Single-Electron Transfer in the Reactions of Unhindered Saturated Primary Alkyl Iodides with Lithium Aluminum Hydride. Reactions of 1-Halooctanes with Lithium Aluminum Deuteride
Welder, Catherine O.,Ashby
, p. 4829 - 4833 (1997)
Evidence for single-electron transfer (SET) in the reactions of lithium aluminum hydride (LAH) with unhindered, saturated primary alkyl halides has not been available. In this study, experiments have been carried out that provide convincing evidence that the unhindered, saturated primary alkyl iodide 1-iodooctane reacts with lithium aluminum deuteride (LAD) in a 1:0.2 ratio to form 1-deuteriooctane with up to 38% incorporation of protium. Since the protium incorporation increased as the reaction proceeded, studies involving the reaction of 1-iodooctane with AlD3 (one of the byproducts in the reaction of LAD with alkyl halides) were carried out in order to determine the effect of AlD3. With AlD3, protium incorporations as high as 84% were observed, indicating that the reaction of AlD3 with 1-iodooctane proceeds via a pathway that involves at least 84% radical formation. The study also included the effect of reaction vessel surface, concentration, and leaving group on the course of the reaction. Factors previously suggested by Newcomb to explain the results of the reactions of LiAlH4 with cyclizable radical probes, e.g., a halogen atom radical-chain process, can be excluded as a valid argument in the present study.
