First Enantioselective Synthesis of Vinyl Oxiranes from Aldehydes and Ylides Generated from Allyl Halides and Chiral Sulfides

• Published in: Journal of organic chemistry Vol. 67; no. 25; pp. 9083 - 9086
• Main Authors: Zanardi, Jacques, Lamazure, David, Minière, Stéphanie, Reboul, Vincent, Metzner, Patrick
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 13-12-2002
• Subjects: Chemistry; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Organic chemistry; Preparations and properties; One pot reaction; Five membered ring; Enantioselectivity; Benzaldehyde; Aldehyde; Oxygen heterocycle; Iodine Organic compounds; Organic sulfide; Allylation; Ylide; Sulfur heterocycle; Caustic soda; Asymmetric synthesis; Vinylic compound; Epoxide; Aromatic compound; Ethylene oxide; Chemical synthesis; Ethylenic compound
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo026085z

Asymmetric allylidenation of aldehydes with sulfur ylides is possible with proper substitution of the initial sulfide, to avoid the [2,3] sigmatropic rearrangement of the unsaturated ylides. One-pot reaction of (2R,5R)-dimethylthiolane with allyl halides, aldehydes, and sodium hydroxide in tert-butyl alcohol affords vinyl oxiranes in good yields. Enantiomeric excesses up to 90% and trans selectivities have been achieved with methallyl-type halides.