2,3-anhydro-4,5:6,7-di-O-isopropylidene-β-D-glycero-D-galacto-oct-4-ulo-4,8-pyranose | 195523-36-5

• 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: 2,3-anhydro-4,5:6,7-di-O-isopropylidene-β-D-glycero-D-galacto-oct-4-ulo-4,8-pyranose
• 英文别名: [(2S,3R)-3-[(1R,2S,6S,9R)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-6-yl]oxiran-2-yl]methanol
• CAS: 195523-36-5
• 化学式: C₁₄H₂₂O₇
• 分子量: 302.324
• InChiKey: SPLCXXYWZJCJHV-ZIBJRRCSSA-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：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  78.9
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,3-anhydro-4,5:6,7-di-O-isopropylidene-β-D-glycero-D-galacto-oct-4-ulo-4,8-pyranose 在 红铝 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 4.0h， 以90%的产率得到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
• 作为产物：
  描述：

  2,3:4,5-bis-O-(isopropylidene)-D-fructopyranose aldehyde 在 锂硼氢 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 73.0h， 生成 2,3-anhydro-4,5:6,7-di-O-isopropylidene-β-D-glycero-D-galacto-oct-4-ulo-4,8-pyranose
  参考文献：
  名称：

  4-辛糖的合成。第7部分：2,3-脱水糖衍生物作为糖β-内酰胺制备中的关键中间体的高度立体选择性合成

  摘要：

  任一反应1或4与（Ñ，Ñ -dibenzylcarbamoylmethylene）dimethylsulfurane 2在DMSO中，得到2,3-脱水-4,5- ö异亚丙基D-阿拉伯-pentonamide 3或Ñ，ñ二苄2,3-脱水-4,5：6,7-二-O-异亚丙基-β-d-甘油-d-半乳糖基-oct-4-ulo-4,8-​​吡喃磺酰胺5。3和5的配置在第一种情况下是根据其光谱数据确定的，并通过化学转化为已知的2,3-脱水-4,5：6,7- di - O-异亚丙基-β-d-甘油-d-半乳清-oct-4-ulo-4,8-​​吡喃糖11。的治疗3和5与六甲基二锂在THF中所提供的相应的糖β-内酰胺12，13和14分别。

  DOI：

  10.1016/s0957-4166(00)00421-3

文献信息

• 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.
• Synthesis of 4-octuloses. Part 7: Highly stereoselective synthesis of 2,3-anhydrosugar derivatives as key intermediates in the preparation of sugar β-lactams
  作者：Isidoro Izquierdo、Maria T Plaza、Rafael Robles、Antonio J Mota

  DOI：10.1016/s0957-4166(00)00421-3

  日期：2000.11

  Reaction of either 1 or 4 with (N,N-dibenzylcarbamoylmethylene)dimethylsulfurane 2 in DMSO afforded 2,3-anhydro-4,5-O-isopropylidene-d-arabino-pentonamide 3 or N,N-dibenzyl 2,3-anhydro-4,5:6,7-di-O-isopropylidene-β-d-glycero-d-galacto-oct-4-ulo-4,8-pyranosonamide 5, respectively. The configurations of 3 and 5 were determined on the basis of their spectroscopic data, in the first case, and by chemical

  任一反应1或4与（Ñ，Ñ -dibenzylcarbamoylmethylene）dimethylsulfurane 2在DMSO中，得到2,3-脱水-4,5- ö异亚丙基D-阿拉伯-pentonamide 3或Ñ，ñ二苄2,3-脱水-4,5：6,7-二-O-异亚丙基-β-d-甘油-d-半乳糖基-oct-4-ulo-4,8-​​吡喃磺酰胺5。3和5的配置在第一种情况下是根据其光谱数据确定的，并通过化学转化为已知的2,3-脱水-4,5：6,7- di - O-异亚丙基-β-d-甘油-d-半乳清-oct-4-ulo-4,8-​​吡喃糖11。的治疗3和5与六甲基二锂在THF中所提供的相应的糖β-内酰胺12，13和14分别。