title: High 1,3-trans stereoselectivity in nucleophilic substitution at the anomeric position and β-fragmentation of the primary alkoxyl radical in 3-amino-3-deoxy-ribofuranose derivatives: application to the synthesis of 2-epi-(-)-jaspine B.
abstract: The high inverse stereoselectivity in the nucleophilic substitution at the anomeric position of 3-amino-3-deoxy-ribofuranose derivatives is reported. This unprecedented stereoselectivity is explained in terms of preferential nucleophilic attack on the "inside face" of the respective five-membered ring oxocarbenium ion that orients pseudoequatorially to the benzylamine group placed at the C-3 position. In addition, an unusual β-fragmentation of a primary alkoxyl radical generated from its corresponding N-phthalimide derivative was achieved, and thus taking advantages of both reactions, the total synthesis of 2-epi-(-)-jaspine B was completed.
authors.affiliation: Centro de Investigación de la Facultad de Ciencias Químicas, BUAP. 14 Sur Esq. San Claudio, San Manuel 72570, Puebla, México.
authors.forename: Alma
authors.initials: A
authors.lastname: Sánchez-Eleuterio
authors.forename: Leticia
authors.initials: L
authors.lastname: Quintero
authors.forename: Fernando
authors.initials: F
authors.lastname: Sartillo-Piscil
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis / Q000737:chemistry*; D000606:Amino Sugars / Q000737:chemistry*; D008968:Molecular Conformation; D013110:Sphingosine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: C561692:3-amino-3-deoxy-ribofuranose; D000438:Alcohols; D000606:Amino Sugars; C059688:alkoxyl radical; C468594:pachastrissamine; D013110:Sphingosine