gamma-hydroxy unsaturated nitriles: chelation-controlled conjugate additions.
[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.
Fleming
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Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282-1530, USA. fleming@duq.edu
Wang
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Steward
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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
D007202:Indicators and Reagents; D009570:Nitriles