title: Conversion of D-glucose to cyclitol with hydroxymethyl substituent via intramolecular silyl nitronate cycloaddition reaction: application to total synthesis of (+)-cyclophellitol.
abstract: [reaction: see text] A diastereoisomeric mixture of 1-nitro-6-heptene-2,3,4,5-tetraol derivative (A) was prepared by Henry reaction between d-glucose-based aldehyde and nitromethane. Only the (2S)-isomer of A led to cyclitol (B) via nitronate-olefin cycloaddition on treatment with TMS-Cl and Et(3)N in the presence of catalytic DMAP followed by acid treatment. (+)-Cyclophellitol (1) was synthesized from B in eight steps.
authors.affiliation: Department of Bioscience and Biotechnology, School of Engineering and School of Education, Okayama University, Tsushima, Okayama, Japan 700-8530.
authors.forename: Teruhiko
authors.initials: T
authors.lastname: Ishikawa
authors.forename: Yoshihiro
authors.initials: Y
authors.lastname: Shimizu
authors.forename: Takayuki
authors.initials: T
authors.lastname: Kudoh
authors.forename: Seiki
authors.initials: S
authors.lastname: Saito