Construction of 2, 6, 9, 11-tetraoxatricyclo[6.2.1.03, 8]undecane containing 4-keto-d-glucose skeleton. Issue 51 (21st December 2017)

• Record Type: Journal Article
• Authors: Fujitani, Ban; Hanaya, Kengo; Higashibayashi, Shuhei; Shoji, Mitsuru; Sugai, Takeshi
• Is Part Of: Tetrahedron. Volume 73:Issue 51(2017)
• Page Start: 7217
• Page End: 7222
• Publication Date: 2017-12-21
• Subjects: Natural product synthesis -- Tricyclic bisacetal -- Spirolactone -- Cotylenin A -- Acyl migration -- 4-Ketoglucoside; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tet.2017.11.008
• Languages: English
• ISSNs: 0040-4020

Abstract

Abstract: A unique tricyclic bisacetal, 2, 6, 9, 11-tetraoxatricyclo[6.2.1.0 3, 8 ]undecane observed in cotylenin A, was constructed in a simplified model compound, based on 6- O -methyl-4-keto-d -glucose as the scaffold to control of the stereochemistry. The key compound was an unprecedented spirolactone formed from the α-(α′-hydroxy)acyloxy dimethyl acetal, accompanied with stereoselective migration of an acyl group. Subsequent intramolecular acetalization between the hydroxy group at the C-3 and the C-1′ hemiacetal position furnished the desired tricyclic bisacetal. Graphical abstract: