Total synthesis of the methyl glycoside of bradyrhizose via intramolecular pinacol coupling. (14th September 2022)

• Record Type: Journal Article
• Authors: Matsushima, Yoshitaka; Ito, Yutaro; Konno, Hiroyuki
• Is Part Of: Tetrahedron letters. Volume 106(2022)
• Publication Date: 2022-09-14
• Subjects: Bradyrhizose -- Carbocyclic monosaccharide -- Intramolecular pinacol coupling -- Total synthesis; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2022.154060
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Highlights: Bradyrhizose, a unique carbocyclic monosaccharide, plays a key role nitrogen-fixing on some certain semi-aquatic species. A novel and effective synthesis of bradyrhizose as its methyl glycoside was achieved. An efficient synthetic method using intramolecular pinacol coupling as a key reaction was developed (total 16% yield in 15 steps). Abstract: An efficient route for synthesizing bradyrhizose, a unique carbocyclic monosaccharide, as its methyl glycoside has been developed. The formation of the unusual 6-membered carbocyclic ring of bradyrhizose is constructed via the key intramolecular pinacol coupling of the keto aldehyde intermediate. The precursor was easily derived from the known appropriately protected d -glucose via chain elongation and Sharpless asymmetric dihydroxylation.