On the mechanism of carboxylate elimination from carbohydrate monoester-derived radicals

Turner, Julia A.; Zipse, Hendrik und Taylor, Mark S. (2024): On the mechanism of carboxylate elimination from carbohydrate monoester-derived radicals. In: Organic & Biomolecular Chemistry, Bd. 22, Nr. 16: S. 3225-3229

Abstract

A computational study of the mechanism of hydrogen atom transfer-induced carboxylate elimination from monoacylated 1,2-diol groups in pyranosides is presented. A comprehensive analysis of the 1,2-migration, elimination and fragmentation pathways reveals that concerted elimination via a 7-membered, hydrogen-bonded transition state is favored. Relative rates of elimination inferred from an intramolecular competition experiment are consistent with the trends obtained from the calculations.

• Dokumententyp: Zeitschriftenartikel
• Fakultät: Chemie und Pharmazie > Department Chemie
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 1477-0520
• Sprache: Englisch