Synthesis of immunostimulatory alpha-C-galactosylceramide glycolipids via Sonogashira coupling, asymmetric epoxidation, and trichloroacetimidate-mediated epoxide opening.
Stereocontrolled syntheses of alpha-C-GalCer (2) and its alpha-C-acetylenic analogue 6 were accomplished in high efficiency by a convergent construction strategy from 1-hexadecene and d-galactose. The key transformations include Sonogashira coupling, Sharpless asymmetric epoxidation, and Et(2)AlCl-catalyzed cyclization of an epoxytrichloroacetimidate to generate protected dihydrooxazine 21.
Department of Chemistry and Biochemistry, Queens College of The City University of New York, Flushing, New York 11367-1597, USA.
Zheng
Z
Liu
Hoe-Sup
HS
Byun
Robert
R
Bittman
D000081:Acetamides; D000276:Adjuvants, Immunologic; D062845:Chloroacetates; D004852:Epoxy Compounds / Q000737:chemistry*; D005699:Galactosylceramides / Q000138:chemical synthesis* / Q000737:chemistry; D006017:Glycolipids / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D013237:Stereoisomerism; D014238:Trichloroacetic Acid / Q000737:chemistry
D000081:Acetamides; D000276:Adjuvants, Immunologic; D062845:Chloroacetates; D004852:Epoxy Compounds; D005699:Galactosylceramides; D006017:Glycolipids; D014238:Trichloroacetic Acid; C009528:trichloroacetamide