5,6,7,9-tetra-O-acetyl-1,2,3-trideoxy-α-D-gluco-non-1-en-4-ulopyranosyl chloride | 199738-50-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 5,6,7,9-tetra-O-acetyl-1,2,3-trideoxy-α-D-gluco-non-1-en-4-ulopyranosyl chloride
• 英文别名: [(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-chloro-6-prop-2-enyloxan-2-yl]methyl acetate
• CAS: 199738-50-6
• 化学式: C₁₇H₂₃ClO₉
• 分子量: 406.817
• InChiKey: CPVFNRUEFXAIAZ-UUAJXVIYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  27
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  5,6,7,9-tetra-O-acetyl-1,2,3-trideoxy-α-D-gluco-non-1-en-4-ulopyranosyl chloride 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 反应 0.75h， 以25%的产率得到Acetic acid (2R,3R,4R,5S,6S)-3,5-diacetoxy-2-acetoxymethyl-6-allyl-tetrahydro-pyran-4-yl ester
  参考文献：
  名称：

  A stereocontrolled radical access to C-allyl β-D-glycopyranosides from glycopyranosylidene dihalides found en route to C-glycodienes

  摘要：

  Application of the Keck reaction to peracetylated glycopyranosylidene dihalides under mild conditions led efficiently to chloro C-allyl glycosides which were converted to either the corresponding C-allyl beta-D-glycosides or C-D-glycodienes on treatment with, respectively, tri-n-butyltin hydride and DBU. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)10215-5
• 作为产物：
  描述：

  2,3,4,6-tetra-O-acetyl-1-bromo-β-D-glucopyranosyl chloride 、 烯丙基三丁基锡 在 偶氮二异丁腈 作用下， 以 苯 为溶剂， 反应 0.33h， 生成 5,6,7,9-tetra-O-acetyl-1,2,3-trideoxy-α-D-gluco-non-1-en-4-ulopyranosyl chloride
  参考文献：
  名称：

  Ring-Closing Olefin Metathesis of 3,3′-(D-Glycopyranosylidene)bis(1-propene) Compounds as a Route to Anomeric Spiro Sugars

  摘要：

  New peracetylated 3,3 '-(D-glycopyranosylidene)bis(1-propene), prepared from peracetylated anomeric sugar dihalides and allyltributyltin in excess under UV irradiation conditions (AIBN, ca. 35 degreesC), lent themselves to ring-closing olefin metathesis in the presence of Grubbs' catalyst (6 mol %) to afford the corresponding peracetylated spiro[1,5-anhydro-D-glycopyranositol-1,4 ' -cyclopent-1 ' -enes] (D-gluco: 81%, D-Manno: 89%, D-galacto: 72% isolated yield), which could be deacetylated quantitatively. The bis(allylation) reaction (D-gluco: 40%, D-manno: 34%, D-galacto: 24% isolated yield) was in competition with radical-induced rearrangement and elimination reactions. The last process, found to be favored at higher temperature (80 degreesC), opens an easy route to sugar dienes difficult to prepare otherwise.

  DOI：

  10.1002/1099-0690(200108)2001:15<2939::aid-ejoc2939>3.0.co;2-h

文献信息

• Stereocontrolled Access to Higher Sugars (Non-1-en-4-ulopyranosyl Derivatives) and Glycomimetics [3-(β-D-Glycopyranosyl)-1-propenes and(3Z)-4,8-Anhydro-nona-1,3-dienitols]
  作者：Jean-Pierre Praly、Guo-Rong Chen、Joëlle Gola、Georg Hetzer

  DOI：10.1002/1099-0690(200008)2000:16<2831::aid-ejoc2831>3.0.co;2-0

  日期：2000.8

  Yields vary, depending mainly on the parent sugar configuration (D-gluco: 86%; D-galacto: 51%; D-manno: 31%). The corresponding acetylated α-D-non-1-en-4-ulopyranoses resulting from hydrolysis were obtained as by-products (8−23% yield). Radical reduction of the acetylated α-D-non-1-en-4-ulopyranosyl chlorides, mediated by nBu3SnH, led to glycopyranos-1-yl radicals, the diastereoselective quenching of which

  全乙酰化 1-溴-β-D-吡喃葡萄糖基氯与烯丙基三丁基锡在光解条件下反应，得到相应的乙酰化 α-D-non-1-en-4-ulopyranosyl 氯。产量不同，主要取决于母糖的配置（D-葡萄糖：86%；D-半乳糖：51%；D-甘露糖：31%）。水解产生的相应乙酰化 α-D-non-1-en-4-ulopyranoses 作为副产物获得（8-23% 产率）。由 nBu3SnH 介导的乙酰化 α-D-non-1-en-4-ulopyranosyl 氯化物的自由基还原导致 glycopyranos-1-yl 自由基，其非对映选择性猝灭产生乙酰化 3-(β-D-glycopyranosyl)- 1-丙烯具有良好的总产率（50-57% 产率）。这种方法结合了涉及吡喃糖基自由基的 C-C 和 C-H 键形成反应，构成了乙酰化 3-(β-D-吡喃葡萄糖基)-1-丙烯的更有效途径。没有检测到 3-(α-