title: gamma-hydroxy unsaturated nitriles: chelation-controlled conjugate additions.
abstract: [reaction--see text] Chelation between gamma-hydroxy unsaturated nitriles and Grignard reagents promotes an otherwise difficult anionic conjugate addition reaction. The intermediate chelate is readily generated by deprotonation with t-BuMgCl followed by the addition of a second Grignard reagent that triggers an intramolecular conjugate addition. Structurally diverse Grignard reagents add with equal efficiency, providing an intermediate anion that stereoselectively alkylates BnBr in an overall addition-alkylation reaction.
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282-1530, USA. fleming@duq.edu
authors.forename: F F
authors.initials: FF
authors.lastname: Fleming
authors.forename: Q
authors.initials: Q
authors.lastname: Wang
authors.forename: O W
authors.initials: OW
authors.lastname: Steward
mesh_terms: D015195:Drug Design; D006900:Hydroxylation; D007202:Indicators and Reagents; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D007202:Indicators and Reagents; D009570:Nitriles