Synthesis of L-daunosamine and L-ristosamine glycosides via photoinduced aziridination. Conversion to thioglycosides for use in glycosylation reactions.
Application of photoinduced acylnitrene aziridination to the syntheses of L-daunosamine and L-ristosamine glycosides is reported. Photoreaction of methyl 4-O-azidocarbonyl-2,3,6-trideoxy-L-hex-2-enopyranosides, followed by aziridine opening, leads to 3-amino-3-N-,4-O-carbonyl-2,3,6-trideoxy precursors to the aminosugar methyl glycosides. Conversion of these precursors to their thioglycoside analogues followed by N-acetylation of the carbamate moiety permits high yielding and, in some cases, stereoselective glycosylations using the 1-benzenesulfinylpiperidine-triflic anhydride activation method developed by Crich and co-workers. Glycosylations involving activation with N-iodosuccinimide and silver triflate were also successful, but the stereoselectivities of these reactions in general were lower.
Mendlik
Matthew T
MT
Department of Chemistry, Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, USA.
Tao
Peng
P
Hadad
Christopher M
CM
Coleman
Robert S
RS
Lowary
Todd L
TL
D006595:Hexosamines / Q000138:chemical synthesis*
D006595:Hexosamines; C007217:daunosamine