Stereocontrolled routes to cis-hydroxyamino sugars, Part VII: Synthesis of daunosamine and ristosamine.
The nitrogen of an allylic amine can serve as the fulcrum for stereocontrolled delivery of oxygen to an adjacent trigonal site, and cis-hydroxyamino sugars can thus be prepared. Methods for achieving the complementary procedure, namely, control of the delivery of nitrogen to an adjacent site by an allylic oxygen, are described. For example, treatment of methyl 2,3,6-trideoxy-alpha-L-erythro-hex-2-enopyranoside with trichloroacetonitrile gave an imidate ester which reacted with iodonium dicollidine perchlorate to give 2-trichloromethyl-(methyl 2,3,4,6-tetradeoxy-2-iodo-alpha-L-altropyranosido)-[3,4-d]-2-oxazo line. Exhaustive reductive dehalogenation of this product followed by hydrolysis led to methyl N-acetyl-alpha-L-ristosaminide. An analogous series of reactions was used to prepare the corresponding daunosaminide.
D006595:Hexosamines / Q000138:chemical synthesis*; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D009904:Optical Rotation; D013237:Stereoisomerism; D013329:Structure-Activity Relationship
D006595:Hexosamines; D007202:Indicators and Reagents; C007217:daunosamine; C010783:ristosamine