Homochiral cycloadducts derived from sugar aldoximes via nitrone intermediates

• Published in: Tetrahedron Vol. 50; no. 18; pp. 5495 - 5502
• Main Authors: Frederickson, Martyn, Grigg, Ronald, Redpath, James, Thornton-Pett, Mark
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 1994; Elsevier
• Subjects: Chemistry; Chemistry, Organic; Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with n hetero atom and also o and/or s, se, te hetero atoms; Organic chemistry; Organic compounds; Physical Sciences; Physics; Preparations and properties; Science & Technology; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; OXIMES; Oxygen sulfur nitrogen heterocycle; Molecular structure; Sulfone; Overhauser effect; Dialdose; Experimental study; X ray diffraction; Regiospecificity; Diastereoselectivity; Cycloaddition; Vinylic compound; Bicyclic compound; Aldoxime; Organic hydroxylamine; Organic compounds; Crystalline structure
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/S0040-4020(01)80704-3

Tandem nitrone generation/cycloaddition reactions between simple sugar aldoximes and divinyl sulphone in refluxing toluene have been shown to occur regiospecifically and with high diastereoselectivity in the cycloaddition step to afford homochiral cycloadducts in good yield. The process is applicable to both furanose and pyranose aldoximes. Absolute stereochemistries of the products have been determined by NOE spectroscopy and X-ray crystallography. Aldoximes derived from D-galactose and D-ribose react regiospecifically with one mole of divinyl sulphone in toluene at 11O°C to afford good yields of homochiral cycloadducts with high diastereoselectivity.