Protonation of acyllithium reagents by acetonitrile: Synthesis of {beta}-hydroxy nitriles
Journal Article
·
· Journal of Organic Chemistry
- Univ. of Tennessee, Knoxville, TN (United States)
In recent years, the reaction of electrophiles with acyllithium (RCOLi) reagents has been extensively studied and has proven to be a convenient route to acylated products. For example, Seyferth reported that acyllithium reagents, generated in situ from an alkyllithium and carbon monoxide at -110 {degrees}C to -135 {degrees}C, would react with aldehydes, ketones, esters, lactones, isocyanates, isothiocyanates, carbodiimides, carbon disulfide, carbonyl sulfide, organic disulfides, iron pentacarbonyl, and trimethylchlorosilane to give acylated products. Nudelman found that the acyllithium generated from phenyllithium in the presence of alkyl bromides gave diphenylalkylcarbinols. The authors recently reported that trialkylboranes reacted with acyllithium reagents to afford ketones in modest yields. Although Seyferth predicted that acyl anion reagents might react with nitriles to afford addition products such as {alpha}-diketones, no report of a reaction of acyl anion reagents with nitriles has appeared in literature. Recently, the authors reported the first example of the protonation of acyllithium reagents by dichloromethane and dichloroarylmethane. The reaction affords the corresponding {alpha}, {alpha}-dichloro alcohols in excellent yields. The authors wish to report a new synthesis of {beta}-hydroxy nitriles which is based on the reaction of acyllithium with acetonitrile, Scheme 1. 1 tab.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 468740
- Journal Information:
- Journal of Organic Chemistry, Journal Name: Journal of Organic Chemistry Journal Issue: 18 Vol. 60; ISSN 0022-3263; ISSN JOCEAH
- Country of Publication:
- United States
- Language:
- English
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