Acetic acid (2S,3R,4S,5R,6S)-4-(tert-butyl-dimethyl-silanyloxy)-2-iodomethyl-6-(naphthalen-2-yloxy)-5-phenylsulfanyl-tetrahydro-pyran-3-yl ester | 136174-82-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Acetic acid (2S,3R,4S,5R,6S)-4-(tert-butyl-dimethyl-silanyloxy)-2-iodomethyl-6-(naphthalen-2-yloxy)-5-phenylsulfanyl-tetrahydro-pyran-3-yl ester
• CAS: 136174-82-8
• 化学式: C₃₀H₃₇IO₅SSi
• 分子量: 664.677
• InChiKey: GJOODFOXGDIRSP-XYPQWYOHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.86
• 重原子数：
  38.0
• 可旋转键数：
  8.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  Acetic acid (2S,3R,4S,5R,6S)-4-(tert-butyl-dimethyl-silanyloxy)-2-iodomethyl-6-(naphthalen-2-yloxy)-5-phenylsulfanyl-tetrahydro-pyran-3-yl ester 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 生成 2-naphthyl 4-O-acetyl-3-O-((tert-butyldimethyl)silyl)-2,6-dideoxy-β-D-gluco-pyranoside
  参考文献：
  名称：

  A highly stereoselective synthesis of aryl 2-deoxy-.beta.-glycosides via the Mitsunobu reaction

  摘要：

  A highly stereoselective (6.5- > 20:1) synthesis of aryl 2-deoxy-beta-D-glycosides is described. This method involves the Mitsunobu coupling of phenols and 2-alpha-(thiophenyl)- or 2-alpha-(selenophenyl)-alpha-D-pyranoses 3-6, 18, and 19 followed by Bu3SnH reduction of the PhS- and PhSe-groups.

  DOI：

  10.1021/jo00020a003
• 作为产物：
  描述：

  2-naphthyl 4-O-acetyl-3-O-((tert-butyldimethyl)silyl)-2-deoxy-2-(thiophenyl)-6-O-tosyl-D-gluco-pyranose 在 sodium iodide 作用下， 以 四氢呋喃 为溶剂， 以96%的产率得到Acetic acid (2S,3R,4S,5R,6S)-4-(tert-butyl-dimethyl-silanyloxy)-2-iodomethyl-6-(naphthalen-2-yloxy)-5-phenylsulfanyl-tetrahydro-pyran-3-yl ester
  参考文献：
  名称：

  Studies on the Synthesis of Aureolic Acid Antibiotics: Highly Stereoselective Synthesis of Aryl 2-Deoxy-.beta.-glycosides via the Mitsunobu Reaction and Synthesis of the Olivomycin A-B Disaccharide

  摘要：

  The Mitsunobu reaction of phenols and 1,2-cis-2-thiophenyl-alpha-D-glycopyranoses or 1,2-cis-2-selenophenyl-alpha-D-glycopyranoses is a very effective method for the highly stereoselective synthesis of aryl 2-deoxy-beta-D-glycosides. The equatorial 2-thiophenyl or 2-selenophenyl- substituents are easily removed by Bu(3)SnH reduction following the glycosidation reaction to provide the aryl 2-deoxy-beta-D-glycosides in good to excellent yield. The aryl beta-D-glycosides are obtained with 6.5:1 selectivity in the least selective case(Table 1) and up to >20:1 selectivity in others. The reaction appears to be S-N(2)-like in character (see 30), in that the beta:alpha reaction stereoselectivity correlates well with the alpha:beta anomeric composition of the pyranose starting material. The equatorial 2-thiophenyl or 2-selenophenyl substituents play an important role by increasing the alpha:beta anomer ratio of the pyranose starting materials. The reactions do not appear to proceed by way of free oxonium ions such as 17, since several reactions in which 17 was deliberately generated (e.g., TMS-OTf promoted reactions of glycosyl acetate 14, BF3 . Et(2)O catalyzed reactions of imidate 15) gave at best 1:1 mixtures of alpha- and beta-glycosides, and in several cases gave alpha-glycosides with >10:1 selectivity. These data also rule out the involvement of episulfonium ion 18 as a kinetically significant intermediate in reactions that proceed by way of oxonium ion 17. A short and highly effective synthesis of reducing disaccharide 53 from D-fucal was developed. This functionalized disaccharide readily undergoes Mitsunobu glycosidation with 2-naphthol, providing the model naphthyl A-B disaccharide 5 with 11:1 beta,alpha:alpha,alpha selectivity. Finally, olivin precursor 63 has also been glycosylated with 53, providing the advanced synthetic intermediate 6 with excellent diastereoselectivity.

  DOI：

  10.1021/ja00113a013