title: Unsaturated nitriles: stereoselective MgO eliminations.
abstract: 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.
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282-1530, USA. fleming@duq.edu
authors.forename: Fraser F
authors.initials: FF
authors.lastname: Fleming
authors.forename: Brian C
authors.initials: BC
authors.lastname: Shook
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D007659:Ketones / Q000737:chemistry; D008277:Magnesium Oxide / Q000737:chemistry*; D009570:Nitriles / Q000138:chemical synthesis*; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D007659:Ketones; D009570:Nitriles; D008277:Magnesium Oxide