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C-metalated nitriles: electrophile-dependent alkylations and acylations
Journal article   Open access   Peer reviewed

C-metalated nitriles: electrophile-dependent alkylations and acylations

Fraser F Fleming, Zhiyu Zhang, Guoqing Wei and Omar W Steward
Journal of organic chemistry, v 71(4), pp 1430-1435
17 Feb 2006
DOI: https://doi.org/10.1021/jo052102j
PMID: 16468790
Featured in Collection :   UN Sustainable Development Goals @ Drexel
url
https://europepmc.org/articles/pmc1896272?pdf=renderView
Accepted (AM)Open Access (License Unspecified),  Open

Abstract

Acylation Alkylation Magnesium - chemistry Metals - chemistry Nitriles - chemical synthesis Stereoisomerism
Sequential carbonyl addition-conjugate addition of Grignard reagents to 3-oxocyclohex-1-ene-1-carbonitrile generates C-magnesiated nitriles whose alkylation stereoselectivities intimately depend on the nature of the electrophile. The alkylation of these C-magnesiated nitriles with alkyl halides, sulfonates, and unstrained ketones occurs with the retention of the C-Mg configuration, whereas aldehyde and acyl cyanide acylations proceed with inversion of the stereochemistry. Mechanistic probes indicate that the stereoselectivity is controlled by stereoelectronic effects for most electrophiles, except allylic, benzylic, and cyclopropyl halides where single-electron-transfer processes intervene. Screening numerous alkylations of C-magnesiated nitriles with a diverse range of electrophiles reveals the reaction scope and delineates the fundamental stereoelectronic effects responsible for the highly unusual electrophile-dependent alkylations.

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Web of Science research areas
Chemistry, Organic
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