2-deoxy-4,5:6,7-di-O-isopropylidene-β-D-manno-oct-4-ulo-4,8-pyranose | 195523-27-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 2-deoxy-4,5:6,7-di-O-isopropylidene-β-D-manno-oct-4-ulo-4,8-pyranose
• 英文别名: (1R)-1-[(1R,2S,6S,9R)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-6-yl]propane-1,3-diol
• CAS: 195523-27-4
• 化学式: C₁₄H₂₄O₇
• 分子量: 304.34
• InChiKey: NQRQVLKEFOWEFJ-YBRCUDMCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  86.6
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-deoxy-4,5:6,7-di-O-isopropylidene-β-D-manno-oct-4-ulo-4,8-pyranose 在 palladium on activated charcoal 吡啶 、 4-二甲氨基吡啶 、 sodium azide 、 氢气 、 sodium acetate 、 碳酸氢钠 、 溶剂黄146 、 对甲苯磺酰氯 作用下， 以 甲醇 、 乙醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 25.0~100.0 ℃ 、517.1 kPa 条件下， 反应 128.0h， 生成 (1R,6R,7R,8R,8aR)-octahydroindolizine-1,6,7,8-tetraol
  参考文献：
  名称：

  A new and highly stereoselective synthesis of polyhydroxyindolizidines from 4-octulose derivatives

  摘要：

  (1S,2S,6R,7R,8R,8aR)-1,2,6,7,8-五羟基吲哚齐啶（12）和(1R,6R,7R,8R,8aR)-1,6,7,8-四羟基吲哚齐啶（1,6-去环化合欢啶，24）已从重要关键中间体1,4-去氧-1,4-亚胺基-D-赤-L-阿洛-octitol（7）和1,2,4-三去氧-1,4-亚胺基-D-甘露糖基-D-塔罗-octitol（20）中以三步法立体选择性地合成。化合物7和20分别以四步法从2,3:4,5:6,7-三-O-异丙叉基-D-甘露糖基-D-半乳糖-oct-4-ulo-4,8-吡喃糖（1）和2-deoxy-4,5:6,7-二-O-异丙叉基-D-甘露糖-oct-4-ulo-4,8-吡喃糖（13）中容易获得。版权：1998 Elsevier Science Ltd. 保留所有权利。

  DOI：

  10.1016/s0957-4166(98)00064-0
• 作为产物：
  描述：

  2,3:4,5-bis-O-(isopropylidene)-D-fructopyranose aldehyde 在 lithium aluminium tetrahydride 、 碘 、 锌 作用下， 以 1,4-二氧六环 、 乙醚 为溶剂， 反应 1.5h， 生成 2-deoxy-4,5:6,7-di-O-isopropylidene-β-D-manno-oct-4-ulo-4,8-pyranose
  参考文献：
  名称：

  Synthesis of 2-deoxy-4-octulose derivatives by highly diastereoselective alkylations of protected hexuloses

  摘要：

  Reformatsky reaction of 2,3:4,5-di-O-isopropylidene-beta-D-arabino-hexos-2- ulopyranose 1 with methyl bromoacetate proceeded with high diastereoselectivity to give methyl 2-deoxy-4,5:6,7-di-O-isopropylidene-beta-D-manno-oct-4-ulo-4,8-pyranosonate 2 and its -D-gluco isomer 3, in an similar or equal to 10:1 ratio. Configurations of the new stereogenic centres (C-3) in 2 and 3 were determined by reduction of their ester groups to the related 2-deoxy-4,5:6,7-di-O-isopropylidene-beta-D-manno- 4 and -D-gluco-oct-4-ulo-4,8-pyranose 5, respectively. When alkylation at C-1 of 1 was carried out with 2-lithio tert-butyl acetate, the corresponding tert-butyl ester of 2 (6) and 3 (7) were formed in an similar or equal to 5.4:1 ratio. The stereochemistry of 6 and 7 was established by their respective reductions to 4 and 5. On the other hand, reaction of 1 with methyl methoxycarbonylmethylenedimethylsulfurane gave only methyl 2,3-anhydro-4,5:6,7-di-O-isopropylidene-beta-D-glycero-D-galacto-oct-4-ulo-4,8-pyranosonate 8, whose stereochemistry was demonstrated by its transformation to 4. On the other hand, Reformatsky reaction of 2,3:4,6-di-O-isopropylidene-alpha-L-xylo-hexos-2-ulofuranose 10 with methyl bromoacetate proceeded with moderate diastereoselectivity to give methyl 2-deoxy-4,5:6,8-di-O-isopropylidene-alpha-L-gulo-oct-4-ulo-4,7-furanosonate 11 and its -L-ido isomer 12, in an similar or equal to 3.5:1 ratio. Configuration of the new stereogenic centre (C-3) in 11, and hence in 12, was determined by degradation to the known dimethyl D-methoxymalate (+)-13. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00266-8

文献信息

• A new and highly stereoselective synthesis of polyhydroxyindolizidines from 4-octulose derivatives
  作者：Isidoro Izquierdo、Maria T Plaza、Rafael Robles、Antonio J Mota

  DOI：10.1016/s0957-4166(98)00064-0

  日期：1998.3

  (1S,2S,6R,7R,8R,8aR)-1,2,6,7,8-Pentahydroxyindolizidine 12 and (1R,6R,7R,8R,8aR)-1,6,7,8-tetrahydroxyindolizidine (1,6-diepicastanospermine, 24) have been stereoselectively synthesized from the important key intermediates 1,4-dideoxy-1,4-imino-D-erythro-L-altro-octitol 7 and 1,2,4-trideoxy-1,4-imino-D-glycero-D-talo-octitol 20 in three steps. Compounds 7 and 20 were readily obtained from 2,3:4,5:6,7-tri-O-isopropylidene-beta-D-glycero-D-galacto-oct-4-ulo-4,8-pyranose 1 and 2-deoxy-4,5:6,7-di-O-isopropylidene-beta-D-manno-oct-4-ulo-4,8-pyranose 13 in four steps, respectively. (C) 1998 Elsevier Science Ltd. All rights reserved.

  (1S,2S,6R,7R,8R,8aR)-1,2,6,7,8-五羟基吲哚齐啶（12）和(1R,6R,7R,8R,8aR)-1,6,7,8-四羟基吲哚齐啶（1,6-去环化合欢啶，24）已从重要关键中间体1,4-去氧-1,4-亚胺基-D-赤-L-阿洛-octitol（7）和1,2,4-三去氧-1,4-亚胺基-D-甘露糖基-D-塔罗-octitol（20）中以三步法立体选择性地合成。化合物7和20分别以四步法从2,3:4,5:6,7-三-O-异丙叉基-D-甘露糖基-D-半乳糖-oct-4-ulo-4,8-吡喃糖（1）和2-deoxy-4,5:6,7-二-O-异丙叉基-D-甘露糖-oct-4-ulo-4,8-吡喃糖（13）中容易获得。版权：1998 Elsevier Science Ltd. 保留所有权利。
• Synthesis of 2-deoxy-4-octulose derivatives by highly diastereoselective alkylations of protected hexuloses
  作者：Isidoro Izquierdo、María T. Plaza、Rafael Robles、Antonio Mota

  DOI：10.1016/s0957-4166(97)00266-8

  日期：1997.8

  Reformatsky reaction of 2,3:4,5-di-O-isopropylidene-beta-D-arabino-hexos-2- ulopyranose 1 with methyl bromoacetate proceeded with high diastereoselectivity to give methyl 2-deoxy-4,5:6,7-di-O-isopropylidene-beta-D-manno-oct-4-ulo-4,8-pyranosonate 2 and its -D-gluco isomer 3, in an similar or equal to 10:1 ratio. Configurations of the new stereogenic centres (C-3) in 2 and 3 were determined by reduction of their ester groups to the related 2-deoxy-4,5:6,7-di-O-isopropylidene-beta-D-manno- 4 and -D-gluco-oct-4-ulo-4,8-pyranose 5, respectively. When alkylation at C-1 of 1 was carried out with 2-lithio tert-butyl acetate, the corresponding tert-butyl ester of 2 (6) and 3 (7) were formed in an similar or equal to 5.4:1 ratio. The stereochemistry of 6 and 7 was established by their respective reductions to 4 and 5. On the other hand, reaction of 1 with methyl methoxycarbonylmethylenedimethylsulfurane gave only methyl 2,3-anhydro-4,5:6,7-di-O-isopropylidene-beta-D-glycero-D-galacto-oct-4-ulo-4,8-pyranosonate 8, whose stereochemistry was demonstrated by its transformation to 4. On the other hand, Reformatsky reaction of 2,3:4,6-di-O-isopropylidene-alpha-L-xylo-hexos-2-ulofuranose 10 with methyl bromoacetate proceeded with moderate diastereoselectivity to give methyl 2-deoxy-4,5:6,8-di-O-isopropylidene-alpha-L-gulo-oct-4-ulo-4,7-furanosonate 11 and its -L-ido isomer 12, in an similar or equal to 3.5:1 ratio. Configuration of the new stereogenic centre (C-3) in 11, and hence in 12, was determined by degradation to the known dimethyl D-methoxymalate (+)-13. (C) 1997 Elsevier Science Ltd.