title: Synthesis of branched iminosugars through a hypervalent iodine(III)-mediated radical-polar crossover reaction.
abstract: The synthesis of a novel type of branched iminosugars is described. This synthetic strategy is based on two key reactions: first, an aldol reaction with formaldehyde in order to introduce selectively the hydroxymethyl branch, and second, a tandem β-fragmentation-intramolecular cyclization reaction. The combination of both reactions afforded a battery of compounds exhibiting a great structural complexity, with the concomitant formation of a quaternary center, starting from readily available aldoses. With this approach we have demonstrated the usefulness of the fragmentation of anomeric alkoxyl radicals (ARF) promoted by the PhIO/I2 system for the preparation of new compounds with potential interest for both medicinal and synthetic chemists.
authors.affiliation: Instituto de Productos Naturales y Agrobiología del CSIC, Avenida Astrofísico Francisco Sánchez 3, 38206 La Laguna, Tenerife, Spain.
authors.forename: Andrés G
authors.initials: AG
authors.lastname: Santana
authors.forename: Nieves R
authors.initials: NR
authors.lastname: Paz
authors.forename: Cosme G
authors.initials: CG
authors.lastname: Francisco
authors.forename: Ernesto
authors.initials: E
authors.lastname: Suárez
authors.forename: Concepción C
authors.initials: CC
authors.lastname: González
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D050111:Imino Sugars / Q000138:chemical synthesis* / Q000737:chemistry; D007455:Iodine / Q000737:chemistry*; D015394:Molecular Structure
chemical_list: D000438:Alcohols; D050111:Imino Sugars; C059688:alkoxyl radical; D007455:Iodine