Conversion of D-glucose to cyclitol with hydroxymethyl substituent via intramolecular silyl nitronate cycloaddition reaction: application to total synthesis of (+)-cyclophellitol

Teruhiko Ishikawa; Yoshihiro Shimizu; Takayuki Kudoh; Seiki Saito

doi:10.1021/ol035424n

Conversion of D-glucose to cyclitol with hydroxymethyl substituent via intramolecular silyl nitronate cycloaddition reaction: application to total synthesis of (+)-cyclophellitol

Org Lett. 2003 Oct 16;5(21):3879-82. doi: 10.1021/ol035424n.

Authors

Teruhiko Ishikawa¹, Yoshihiro Shimizu, Takayuki Kudoh, Seiki Saito

Affiliation

¹ Department of Bioscience and Biotechnology, School of Engineering and School of Education, Okayama University, Tsushima, Okayama, Japan 700-8530.

PMID: 14535733
DOI: 10.1021/ol035424n

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.