methyl 4,6-O-benzylidene-2-deoxy-2-C-propenyl-α-D-arabino-hexopyranosid-3-ulose | 135759-86-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 4,6-O-benzylidene-2-deoxy-2-C-propenyl-α-D-arabino-hexopyranosid-3-ulose
• 英文别名: Methyl 2-C-allyl-4,6-O-benzylidene-α-D-arabino-hexopyranosid-3-ulose；(2R,4aR,6S,7R,8aR)-6-methoxy-2-phenyl-7-prop-2-enyl-4a,6,7,8a-tetrahydro-4H-pyrano[3,2-d][1,3]dioxin-8-one
• CAS: 135759-86-3
• 化学式: C₁₇H₂₀O₅
• 分子量: 304.343
• InChiKey: RQYXZQKHXVBCBU-CNLQAYEWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.23
• 重原子数：
  22.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  methyl 4,6-O-benzylidene-2-deoxy-2-C-propenyl-α-D-arabino-hexopyranosid-3-ulose 在 lithium aluminium tetrahydride 作用下， 以29%的产率得到methyl 4,6-O-benzylidene-2-deoxy-2-(2-propenyl)-α-D-allohexopyranoside
  参考文献：
  名称：

  Free radical substitutions of acyloxy groups in carbohydrate α-ketoesters

  摘要：

  当在回流苯中并在偶氮异丁腈（AIBN）作为自由基引发剂存在下用三正丁基氢化锡处理时，一系列含有α-酮酯官能团的碳水化合物衍生物会经历酰氧基的有效还原损失；在类似的条件下，但用烯丙基三正丁基锡代替氢化物，会发生有效的α-C-烯丙基化，轴向取代优先发生在酮酯位于构象稳定的吡喃环内的化合物中；该方法代表了碳水化合物衍生物脱氧和引入分支点的新方法。

  DOI：

  10.1039/c39910000690
• 作为产物：
  描述：

  methyl 4,6-O-benzylidene-2-deoxy-2-(2-propenyl)-α-D-allohexopyranoside 在 二甲基亚砜 、 三乙胺 、 三氟乙酸酐 作用下， 生成 methyl 4,6-O-benzylidene-2-deoxy-2-C-propenyl-α-D-arabino-hexopyranosid-3-ulose
  参考文献：
  名称：

  The Stereoselective Preparation of an Enantiomerically Pure Cyclopentane Using Intramolecular Aldol Cyclopentaannulation of a Glucose Derivative

  摘要：

  Methods for the annulation of carbohydrates have found extensive applications in organic synthesis. We report here a new protocol for the stereoselective conversion of glucose into an enantiomerically pure cyclopentane aldehyde 22. The readily available epoxide 15 was reacted with allyl Grignard to produce alcohol 16 in 86% yield. Swern oxidation followed by epimerization using triethylamine in N,N-dimethylformamide furnished the ketone 17 also in 86% yield. Regioselective deprotonation with lithium hexamethyldisilazane in THF was followed by methylation with methyl iodide and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidone as cosolvent to give 80% yield of ketone 18. Oxidation of ketone 18 by the Wacker procedure gave the 1,4-diketone 19 in 56% yield. Intramolecular aldol condensation occurred readily on treatment of diketone 19 with potassium tert-butoxide in toluene to furnish a 90% yield of enone 20. Treatment with N-bromosuccinimide produced the bromoester 21 in 72% yield, which was reduced to a mixture of aldehydes 22 (61%) and 23 (14%) with zinc shot in 2-propanol.

  DOI：

  10.1021/jo981225j

文献信息

• Claisen rearrangement of hexenopyranoside allyl ethers: A new approach to α-branched-chain dicarbonyl sugars
  作者：Kimiaki Furuichi、Hiromasa Hashimoto、Toshio Miwa

  DOI：10.1016/0008-6215(91)80006-9

  日期：1991.11

  corresponding allyl ethers. Oxidation of the allyl ethers, followed by thermal elimination and rearrangement, gave C -allylhexosuloses in good yield. Rearrangement of ethers 10a and 10c was especially stereoselective, giving axially oriented C -allylhexosulose derivatives, which were readily epimerized to their equatorial isomers in quantitative yield. In the Claisen rearrangement of the crotyl ether 14c ,

  摘要将2，3-脱水吡喃糖苷与苯基硒化钠裂解制备的β-羟基苯基硒化物被定量转化为相应的烯丙基醚。烯丙基醚的氧化，然后进行热消除和重排，以高收率得到C-烯丙基己糖。醚10a和10c的重排特别是立体选择性的，得到轴向取向的C-烯丙基己糖衍生物，其易于以定量产率差向为其赤道异构体。在巴豆醚14c的克莱森重排中，糖的手性转移到新形成的不对称碳原子上。该程序提供了将脱水糖转化为C-烯丙基己糖衍生物的便利方法。