It has been demonstrated by means of spectroscopic studies involving cyclizable alkyl halides that lithium dimethylcuprate can react with organic halides by a single electron transfer pathway. The reaction of lithium diorganocuprates (LiCuR2) with alkyl halides is of major synthetic imp0rtance.l
Evidence for a single electron transfer mechanism in the reduction of benzophenone with lithium alkoxides
โ Scribed by E.C. Ashby; J.N. Argyropoulos
- Publisher
- Elsevier Science
- Year
- 1986
- Tongue
- French
- Weight
- 273 KB
- Volume
- 27
- Category
- Article
- ISSN
- 0040-4039
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โฆ Synopsis
The reduction of benzophenone by lithium alkoxides gives rise to benzophenone ketyl which disappears in a first-order fashion and whose first-order rate constant is approximately equal to the pseudo-first-order rate constant for the formation of the product, benzhydrol.
๐ SIMILAR VOLUMES
Evidence for a radical process in' the reaction of lithium alkoxides with alkyl iodides was obtained by the observation of cyclization of appropriate radical probes, by the trapping of radicals, and by EPR spectroscopic observations relating to the one electron donor properties of alkoxides.
Swmnurz~: EPR evidence supporting a single electron transfer mechanism in the reduction of secondary and tertiary alcohols to hydrocarbons with LiAlH4 is presented.
Summaly: The stereochemical results of the reduction of cyclic ketones with alkoxyaluminium dichlorides do not conform to the conventional polar cyclic mechanism and may be explained by a single electron transfer mechanism.
The widespread use of lithium diisopropyl amide (LDA) as a strong base has revolutionized numerous facets of mechanistic and synthetic organic chemistry in recent years;' however, it is less widely appreciated that amide bases can function also as reducing agents.' LDA, for example, reduces benzophe