title: Fine synthetic nucleoside chemistry based on nucleoside natural products synthesis.
abstract: Synthetic nucleoside chemistry based on nucleoside natural products synthesis were described. First, a samarium diiodide (SmI 2)-promoted aldol reaction with the use of alpha-phenylthioketone as an enolate was developed. The characteristics of this reaction are that the enolate can be regioselectively generated and the aldol reaction proceeds under near neutral condition. This reaction is proved to be a powerful reaction for the synthesis of complex nucleoside natural products, and herbicidin B and fully protected tunicaminyluracil, which were undecose nucleoside natural products, were synthesized. Next, the synthetic methodology of the caprazamycins, which are promising antibacterial nucleoside natural products, was also developed by the strategy including beta-selective ribosylation without using a neighboring group participation. Our synthetic route provided a range of key analogues with partial structures to define the pharmacophore. Simplification of the caprazamycins was further pursued to develop diketopiperazine analogs.
authors.affiliation: Graduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo, Japan. ichikawa@pharm.hokudai.ac.jp
authors.forename: Satoshi
authors.initials: S
authors.lastname: Ichikawa
mesh_terms: D000241:Adenosine / Q000031:analogs & derivatives / Q000138:chemical synthesis; D000900:Anti-Bacterial Agents / Q000138:chemical synthesis; D001426:Bacterial Proteins / Q000737:chemistry / Q000378:metabolism*; D001688:Biological Products / Q000096:biosynthesis / Q000138:chemical synthesis; D002625:Chemistry, Organic; D006575:Heterocyclic Compounds, 3-Ring / Q000138:chemical synthesis; D007454:Iodides / Q000737:chemistry*; D009005:Monosaccharides / Q000096:biosynthesis / Q000378:metabolism; D009705:Nucleosides / Q000096:biosynthesis / Q000138:chemical synthesis*; D009842:Oligopeptides / Q000096:biosynthesis / Q000378:metabolism; D055601:Organic Chemistry Phenomena; D012493:Samarium / Q000737:chemistry*; D013329:Structure-Activity Relationship; D014166:Transferases / Q000737:chemistry / Q000378:metabolism*; D017855:Transferases (Other Substituted Phosphate Groups); D014498:Uracil / Q000031:analogs & derivatives* / Q000138:chemical synthesis
chemical_list: D000900:Anti-Bacterial Agents; D001426:Bacterial Proteins; D001688:Biological Products; D006575:Heterocyclic Compounds, 3-Ring; D007454:Iodides; D009005:Monosaccharides; D009705:Nucleosides; D009842:Oligopeptides; C506201:herbicidin B; C438940:lipid I; C514546:tunicaminyluracil; D012493:Samarium; D014498:Uracil; D014166:Transferases; D017855:Transferases (Other Substituted Phosphate Groups); C079803:mraY protein, Bacteria; D000241:Adenosine; C409809:samarium diiodide