(3Z)-1,6-anhydro-4-O-(tert-butyldiphenylsilyl)-2-O-(1'-ethoxy-2'-iodoethyl)-3-deoxy-3-methoxyimine-β-D-arabino-hexopyranose | 190188-91-1

• 分子结构分类: 有机化合物
• 英文名称: (3Z)-1,6-anhydro-4-O-(tert-butyldiphenylsilyl)-2-O-(1'-ethoxy-2'-iodoethyl)-3-deoxy-3-methoxyimine-β-D-arabino-hexopyranose
• CAS: 190188-91-1
• 化学式: C₂₇H₃₆INO₆Si
• 分子量: 625.576
• InChiKey: QRTWSCVUNYXQRZ-UCGARELFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.87
• 重原子数：
  36.0
• 可旋转键数：
  10.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  67.74
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (3Z)-1,6-anhydro-4-O-(tert-butyldiphenylsilyl)-2-O-(1'-ethoxy-2'-iodoethyl)-3-deoxy-3-methoxyimine-β-D-arabino-hexopyranose 在 偶氮二异丁腈 、 三丁基氯化锡 、 四丁基碘化铵 、 sodium hydride 、 sodium cyanoborohydride 作用下， 以 叔丁醇 为溶剂， 反应 6.0h， 生成 N-[(1R,2S,6S,8R)-7-(tert-Butyl-diphenyl-silanyloxy)-5-methylene-3,10,11-trioxa-tricyclo[6.2.1.0^2,6]undec-6-yl]-O-methyl-hydroxylamine
  参考文献：
  名称：

  Radical cyclisation onto C-3 of 1,6-anhydro-β-d-mannopyranose derivatives. Application to the formation of the C8a centre of (−)-tetrodotoxin

  摘要：

  Starting from 1,6-anhydro-beta-D-mannopyranose, compounds 7a-d, which have a ketoxime ether at C3 and a carbon radical precursor tethered to the hydroxyl group at position 2, were efficiently prepared. While alkyl pi-radicals derived from 7a and 7b failed to cyclize, the vinyl sigma-radicals derived from 7c and 7d underwent the desired 1,5-exo cyclization, affording advanced precursors of (-)-tetrodotoxin. This type of transformation should be useful for the formation of sterically crowded nitrogen-bearing carbon centers in carbohydrate-derived substrates. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00460-7
• 作为产物：
  描述：

  tert-Butyl-((1R,2S,6R,7R,8R)-4,4-dimethyl-3,5,10,11-tetraoxa-tricyclo[6.2.1.0^2,6]undec-7-yloxy)-diphenyl-silane 在 吡啶 、 N-碘代丁二酰亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (3Z)-1,6-anhydro-4-O-(tert-butyldiphenylsilyl)-2-O-(1'-ethoxy-2'-iodoethyl)-3-deoxy-3-methoxyimine-β-D-arabino-hexopyranose
  参考文献：
  名称：

  Radical cyclisation onto C-3 of 1,6-anhydro-β-d-mannopyranose derivatives. Application to the formation of the C8a centre of (−)-tetrodotoxin

  摘要：

  Starting from 1,6-anhydro-beta-D-mannopyranose, compounds 7a-d, which have a ketoxime ether at C3 and a carbon radical precursor tethered to the hydroxyl group at position 2, were efficiently prepared. While alkyl pi-radicals derived from 7a and 7b failed to cyclize, the vinyl sigma-radicals derived from 7c and 7d underwent the desired 1,5-exo cyclization, affording advanced precursors of (-)-tetrodotoxin. This type of transformation should be useful for the formation of sterically crowded nitrogen-bearing carbon centers in carbohydrate-derived substrates. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00460-7

文献信息

• 5-<i>exo</i> Radical Cyclization onto 3-Alkoxyketimino-1,6-anhydromannopyranoses. Efficient Preparation of Synthetic Intermediates for (−)-Tetrodotoxin
  作者：B. Noya、M. D. Paredes、L. Ozores、R. Alonso

  DOI：10.1021/jo000325y

  日期：2000.9.1

  6-anhydro-beta-D-mannopyranose derivatives were found to be useful 5-exo radical traps of alkyl and vinyl radicals generated at a chain tethered to the C2 hydroxyl group, allowing advanced synthetic intermediates for (-)-tetrodotoxin to be prepared from D-mannose in good overall yield.

  发现在1,3,6-脱水-β-D-甘露吡喃糖衍生物的C3处的酮肟醚是有用的5-exo自由基捕集剂，它们在与C2羟基相连的链上产生的烷基和乙烯基自由基，允许用于（-由D-甘露糖制得的β-河豚毒素具有良好的总收率。