C-C Bond Formation by Sequential Intramolecular Hydrogen Atom Transfer/Intermolecular Radical Allylation Reaction in Carbohydrate Systems

• Published in: European journal of organic chemistry Vol. 2012; no. 20; pp. 3818 - 3829
• Main Authors: León, Elisa I., Martín, Ángeles, Pérez-Martín, Inés, Quintanal, Luís M., Suárez, Ernesto
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.07.2012; WILEY‐VCH Verlag; Wiley; Wiley-VCH
• Subjects: C-C coupling; Carbohydrates; Carbohydrates with 4, 5, 6, ... C atoms, dissacharides and oligosaccharides; Carbohydrates. Nucleosides and nucleotides; Chemistry; Chemistry, Organic; Exact sciences and technology; Free radicals chemistry; Hydrogen transfer; Organic chemistry; Physical Sciences; Preparations and properties; Radical all­ylation; Radical reactions; Reactivity and mechanisms; Science & Technology; C-C coupling; Carbohydrates; Hydrogen transfer; PYRANOSE; ALKYLATION; INVERSION; 1,5-HYDROGEN TRANSFER; ABSTRACTION; Radical reactions; STEREOSELECTIVITY; DELTA-CARBON ATOM; RING; CHEMISTRY; Radical all-ylation; ALKOXYL RADICALS; Intramolecular reaction; Molecular structure; Chemical bond; C―C coupling; Oside; Tandem reaction; Free radical reaction; Disaccharide; Allylation; Chemical coupling; Stereoselectivity; Functionalization; Carbon carbon bond; Organic free radical; Radical allylation
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201200300

A tandem 1,5‐, 1,6‐ or 1,8‐intramolecular hydrogen atom transfer (HAT)/intermolecular radical allylation using mono‐ or (1→4)‐O‐disaccharide models is described. It is a simple, sequential, stereocontrolled methodology for C–C bond formation by remote free radical functionalization, giving access to interesting carbohydrate structures carrying differently functionalized tethers. A tandem intramolecular hydrogen atom transfer (HAT)/intermolecular radical allylation is described. This process occurs by a completely regio‐ and stereoselective route that provides a simple methodology for C–C bond formation on remote positions without modifying the remainder of the carbohydrate.