Intramolecular hydrogen abstraction reaction promoted by alkoxy radicals in carbohydrates. Synthesis of chiral 2,7-dioxabicyclo[2.2.1]heptane and 6,8-dioxabicyclo[3.2.1]octane ring systems.
The reaction of specifically protected anhydroalditols with (diacetoxyiodo)benzene or iodosylbenzene and iodine is a mild and selective procedure for the synthesis of chiral 6,8-dioxabicyclo[3.2.1]octane and 2,7-dioxabicyclo[2.2.1]heptane ring systems under neutral conditions. This reaction can be considered to be an intramolecular glycosidation that goes through an intramolecular hydrogen abstraction promoted by an alkoxy radical followed by oxidation of the transient C-radical intermediate to an oxycarbenium ion. This methodology is useful not only for the preparation of chiral synthons but also for the selective oxidation of specific carbons of the carbohydrate skeleton, constituting a good procedure for the synthesis of protected uloses.
Francisco
Cosme G
CG
Instituto de Productos Naturales y Agrobiología del C.S.I.C., Carretera de La Esperanza 3, 38206 La Laguna, Tenerife, Spain.
Herrera
Antonio J
AJ
Suárez
Ernesto
E
D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry; D002241:Carbohydrates / Q000138:chemical synthesis / Q000737:chemistry*; D005609:Free Radicals; D007202:Indicators and Reagents; D008958:Models, Molecular; D008968:Molecular Conformation
D019086:Bridged Bicyclo Compounds, Heterocyclic; D002241:Carbohydrates; D005609:Free Radicals; D007202:Indicators and Reagents