Highly functionalized glyco-conjugated hexahydroazepindiones from saccharide imides via the Norrish type II reaction

• Published in: Carbohydrate research Vol. 341; no. 10; pp. 1543 - 1556
• Main Authors: Stark, Markus, Thiem, Joachim
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 24.07.2006; Elsevier
• Subjects: Alkylation; Azepines - chemistry; Biochemistry & Molecular Biology; Chemistry; Chemistry, Applied; Chemistry, Organic; Glucose - analogs & derivatives; Hexahydroazepinediones; Imides; Life Sciences & Biomedicine; Mannose - analogs & derivatives; Norrish type II; Photochemistry; Physical Sciences; Saccharides; Science & Technology; Succinimides - chemical synthesis; Tosyl Compounds - chemistry; Saccharides; Imides; Norrish type II; Hexahydroazepinediones; SYSTEM; imides; saccharides; ACIDS; hexahydroazepinediones; PHOTOCHEMISTRY; CARBOHYDRATE RADICALS; DERIVATIVES
• ISSN: 0008-6215; 1873-426X
• DOI: 10.1016/j.carres.2006.03.016

Starting from readily available protected 6-tosylates of d-glucose and d-mannose in both their pyranoside and furanoside forms as well as 6-tosylates of α- d-galactopyranose, the corresponding primary succinimido derivatives were obtained in good yield by nucleophilic displacement with potassium succinimide. These imido sugars were photochemically transformed into hexahydroazepindione derivatives such as by means of a Norrish type II reaction. As expected, the intramolecular alkylation proceeded via an 1,6 H-abstraction leading to a stabilized diradical. The regiochemistry of the photoreaction was controlled by configurational, conformational and electronic features and was sometimes influenced by the protecting groups. Using this route, a facile approach to a novel class of highly functionalized sugar derived heterocycles was developed.