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Unsaturated nitriles: stereoselective MgO eliminations
Journal article   Peer reviewed

Unsaturated nitriles: stereoselective MgO eliminations

Fraser F Fleming and Brian C Shook
Journal of organic chemistry, v 67(11), pp 3668-3672
31 May 2002
PMID: 12027678

Abstract

Aldehydes - chemistry Ketones - chemistry Magnesium Oxide - chemistry Nitriles - chemical synthesis Stereoisomerism
Alpha,beta-unsaturated nitriles are readily synthesized by eliminating MgO from beta-hydroxynitriles. Deprotonating acyclic, and cyclic, beta-hydroxynitriles with excess MeMgCl smoothly generates dianion intermediates that eject MgO with concurrent formation of alpha,beta-unsaturated nitriles. Alternatively, sequential addition of lithioacetonitrile and MgBr(2) to aldehydes and ketones generates magnesium alkoxides in situ that eliminate MgO upon addition of MeMgCl. The MeMgCl-induced MgO eliminations smoothly generate alpha,beta-unsaturated nitriles from hindered ketones that are otherwise difficult to synthesize.

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Chemistry, Organic
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