Total Synthesis of the Phenolic Glycolipid Mycoside B and the Glycosylated p‐Hydroxybenzoic Acid Methyl Ester HBAD‐I, Virulence Markers of Mycobacterium tuberculosis. Issue 21 (12th June 2013)

• Record Type: Journal Article
• Authors: Barroso, Santiago; Geerdink, Danny; ter Horst, Bjorn; Casas‐Arce, Eva; Minnaard, Adriaan J.
• Is Part Of: European journal of organic chemistry. Issue 21(2017)
• Page Start: 4642
• Page End: 4654
• Publication Date: 2013-06-12
• Subjects: Natural products -- Carbohydrates -- Glycolipids -- Asymmetric synthesis -- Total synthesis; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201300437
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: The phenolic glycolipid mycoside B, present in Mycobacterium bovis and hypervirulent strains of Mycobacterium tuberculosis, has been synthesized for the first time. Multiple methyl groups were introduced by the extensive use of catalytic asymmetric 1, 4‐addition reactions, asymmetric hydrogenation of a β‐keto ester afforded the basis for the central 1, 3‐diol moiety, and introduction of the 2‐ O ‐methyl‐α‐L ‐rhamnoside unit was achieved by stereoselective glycosylation with p ‐iodophenol and subsequent Sonogashira coupling, providing a basis for the generation of analogues. In addition, the related monosaccharide HBAD‐I, present in the same species, has been efficiently synthesized for the first time by selective methylation of the hydroxy group at C‐2 of a rhamnoside. Abstract : The phenolic glycolipid mycoside B and the related phenolic glycoside HBAD‐I from Mycobacterium tuberculosis have been synthesized for the first time. A highly convergent strategy was used featuring catalytic asymmetric 1, 4‐additions of MeMgBr and Me2 Zn and a late‐stage Sonogashira coupling as the key steps.