2-deoxy-4,5:6,8-di-O-isopropylidene-α-L-gulo-oct-4-ulofuranose | 195523-46-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-deoxy-4,5:6,8-di-O-isopropylidene-α-L-gulo-oct-4-ulofuranose
• 英文别名: (1R)-1-[(1R,2S,6S,8S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[6.4.0.02,6]dodecan-6-yl]propane-1,3-diol
• CAS: 195523-46-7
• 化学式: C₁₄H₂₄O₇
• 分子量: 304.34
• InChiKey: LMYGIECOUAXPCD-FDKVEUBTSA-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-4,5:6,8-di-O-isopropylidene-α-L-gulo-oct-4-ulofuranose 在 palladium on activated charcoal sodium azide 、 水 、 氢气 、 碳酸氢钠 、 sodium carbonate 、 三乙胺 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 20.0~80.0 ℃ 、405.33 kPa 条件下， 反应 111.0h， 生成 N-benzyloxycarbonyl-1,2,4-trideoxy-1,4-imino-L-glycero-D-talo-octitol
  参考文献：
  名称：

  由 L-山梨糖制备的 4-辛酮糖衍生物作为立体选择性合成 C-糖苷和聚羟基吲哚里西啶类似物的关键中间体

  摘要：

  1 和 12 与对甲苯磺酰氯在吡啶中的反应得到相应的 1-Op-甲苯磺酰衍生物 2 和 13，产率分别为 91% 和 60%。通过在无水二氯甲烷中用 I2/Ph3P/咪唑处理，化合物 12 也转化为 14。在 DMF 中用 NaN3 处理化合物 12 和 13/14 得到各自的 1-叠氮基-1-脱氧衍生物 3 和 15，然后将它们去丙酮化得到游离的 4-辛糖 4 和 16。这些随后在存在下氢化10% Pd/C 以提供预期的多羟基化支链吡咯烷 5 和 17。尝试在 N-Cbz 保护的吡咯烷 7 和 19 中的 C-8 处进行 OH OMes 转化不成功，并且发生了内部脱水过程以产生相应的C-糖苷类呋喃糖 9 和 20。 另一方面，

  DOI：

  10.1002/1099-0690(200006)2000:11<2071::aid-ejoc2071>3.0.co;2-a
• 作为产物：
  描述：

  methyl 2-deoxy-4,5:6,8-di-O-isopropylidene-α-L-gulo-oct-4-ulo-4,7-furanosonate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 1.5h， 以84%的产率得到2-deoxy-4,5:6,8-di-O-isopropylidene-α-L-gulo-oct-4-ulofuranose
  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

• 4-Octulose Derivatives, Prepared fromL-Sorbose, as Key Intermediates in the Stereoselective Synthesis ofC-Glycoside and Polyhydroxyindolizidine Analogues
  作者：Isidoro Izquierdo、Maria T. Plaza、Rafael Robles、Antonio J. Mota

  DOI：10.1002/1099-0690(200006)2000:11<2071::aid-ejoc2071>3.0.co;2-a

  日期：2000.6

  unsuccessful and an internal anhydration process took place to yield the corresponding C-glycoside-like furanoses 9 and 20. On the other hand, 23 was transformed into the D-ribo analogue 25 through reduction of the intermediate 4,6-diulose 24. Finally, deprotection of 25 in acid medium to give the free 4-ulose 26, followed by hydrogenation of the latter in the presence of 10% Pd/C in methanol, allowed

  1 和 12 与对甲苯磺酰氯在吡啶中的反应得到相应的 1-Op-甲苯磺酰衍生物 2 和 13，产率分别为 91% 和 60%。通过在无水二氯甲烷中用 I2/Ph3P/咪唑处理，化合物 12 也转化为 14。在 DMF 中用 NaN3 处理化合物 12 和 13/14 得到各自的 1-叠氮基-1-脱氧衍生物 3 和 15，然后将它们去丙酮化得到游离的 4-辛糖 4 和 16。这些随后在存在下氢化10% Pd/C 以提供预期的多羟基化支链吡咯烷 5 和 17。尝试在 N-Cbz 保护的吡咯烷 7 和 19 中的 C-8 处进行 OH OMes 转化不成功，并且发生了内部脱水过程以产生相应的C-糖苷类呋喃糖 9 和 20。 另一方面，
• 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.