methyl (2R,4aR,6S,9aR,9bS)-4,4a,6,8,9a,9b-hexahydro-6-methoxy-8-oxo-2-phenylfuro[2',3':4,5]pyrano[3,2-d]-1,3-dioxin-7-carboxylate | 382591-40-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: methyl (2R,4aR,6S,9aR,9bS)-4,4a,6,8,9a,9b-hexahydro-6-methoxy-8-oxo-2-phenylfuro[2',3':4,5]pyrano[3,2-d]-1,3-dioxin-7-carboxylate
• 英文别名: 4,6-O-benzylidene-α-D-glucopyranoside；methyl 4-methoxy-2-oxo-8-phenyl-1,2,5a,6,9a,9b-hexahydro-4H,8H-7,9-dioxacyclopenta[c]chromene-3-carboxylate；methyl (1S,2R,7S,9R,12R)-7-methoxy-4-oxo-12-phenyl-3,8,11,13-tetraoxatricyclo[7.4.0.02,6]tridec-5-ene-5-carboxylate
• CAS: 382591-40-4
• 化学式: C₁₈H₁₈O₈
• 分子量: 362.336
• InChiKey: LTMJFJDMXDVTCY-HMGGTWIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl (2R,4aR,6S,9aR,9bS)-4,4a,6,8,9a,9b-hexahydro-6-methoxy-8-oxo-2-phenylfuro[2',3':4,5]pyrano[3,2-d]-1,3-dioxin-7-carboxylate 在 水 、 碳酸氢钠 作用下， 以 四氢呋喃 为溶剂， 反应 21.0h， 以55%的产率得到methyl 4,6-O-benzylidene-2-C-methoxycarbonylmethyl-α-D-ribo-hexopyranosid-3-ulose
  参考文献：
  名称：

  Novel autoxidation and Michael addition of a butenolide-containing sugar leading to a C-branched-chain glucopyranosidulose, and X-ray structure of intermediates

  摘要：

  A butenolide-containing sugar available from the aldol condensation of methyl 4,6-O-benzylidene-alpha-D-glucopyranosid-2-ulose with diethyl malonate is autoxidized at the C-3 position into the corresponding alpha,beta-unsaturated gamma-lactone sugar by air, which subsequently undergoes 1,4-conjugate (Michael) addition of hydroxide ion (or water) leading to a C-branched-chain glucopyranosidulose. The autoxidations are also performed in weakly basic, neutral and weakly acidic medium, respectively. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(03)00257-x
• 作为产物：
  描述：

  methyl 4,6-O-benzylidene-α-D-arabino-hexopyranosid-2-ulose 、 丙二酸二乙酯 在 sodium methylate 作用下， 生成 methyl (2R,4aR,6S,9aR,9bS)-4,4a,6,8,9a,9b-hexahydro-6-methoxy-8-oxo-2-phenylfuro[2',3':4,5]pyrano[3,2-d]-1,3-dioxin-7-carboxylate
  参考文献：
  名称：

  4,4-O-亚苄基甲基的新型合成方法[4-脱氧-α-d-阿拉伯糖-己吡喃糖苷-2,2'-咪唑烷]及其同系物和糖-γ-丁内酰胺衍生物-α-d-阿拉伯糖基己吡喃二糖-2-果糖

  摘要：

  新型甲基4,6-O-亚苄基螺[2-脱氧-α-D-阿拉伯糖基-己吡喃糖苷-2,2'-咪唑烷]及其同系物甲基4,6-O-亚苄基-3'，4'，5'，通过4,6-O-亚苄基-α-甲基的反应以高收率合成了6'-四氢-1'H-螺[2-脱氧-α-D-阿拉伯糖基-己吡喃糖苷-2,2'-嘧啶]具有1，2-二氨基乙烷和1，3-二氨基丙烷的D-阿拉伯糖基己基吡喃糖-2-酮糖。结果完全不同于与芳基胺或烷基胺的反应。一锅合成新型（E）-甲基4- [羟基（甲氧基）亚甲基] -5-氧-1-烷基-（4,6-O-亚苄基-2-脱氧-α-D-吡喃葡萄糖基）[3通过烷基胺与含丁烯内酯的糖的反应获得了1,2-b]吡咯烷，该糖衍生自甲基4的醛醇缩合 带有丙二酸二乙酯的6-O-亚苄基-α-D-阿拉伯糖基-吡喃果糖基-2-ulose。这些糖-γ-丁内酰胺衍生物是潜在的GABA受体配体。

  DOI：

  10.1016/j.carres.2010.01.004

文献信息

• Stereoselective synthesis of 2,2-bis(C-branched-chain)glucopyranosid-3-ulose via an autoxidation–Michael addition reaction
  作者：Hong-Min Liu、Fuyi Zhang、Da-Peng Zou

  DOI：10.1039/b306227a

  日期：——

  2,2-Bis(C-branched-chain)glucopyranosid-3-uloses, designed for the preparation of biologically active natural product iridoid derivatives, are synthesized selectively by the new reaction of butenolide-containing sugar with active methylene compounds, and the new reaction is clarified as autoxidation followed by Michael addition of carbanion.

  通过含丁烯内酯的糖与活性亚甲基化合物的新反应，选择性地合成了 2,2-双（C-支链）吡喃葡萄糖苷-3-乌糖，该新反应被明确为自氧化反应，然后是碳离子的迈克尔加成反应。
• Novel Methyl 4,6-O-benzylidene-3-ketoglucopyranosid-fused γ-lactam: Synthesis and Crystal Structure
  作者：Hong Liu、Fuyi Zhang、Jin-Peng Li、Xuebin Yan、Hong-Min Liu、Yu-Fen Zhao

  DOI：10.1007/s10870-011-0079-6

  日期：2011.8

  The title compound methyl 4,6-O-benzylidene-3-ketoglucopyranosid-fused γ-lactam was synthesized from 2-oxoglucopyranoside in one pot via multi-step reaction sequence under mild conditions. It was characterized by HRMS, 1H and 13C-NMR, IR, elemental analysis and single crystal X-ray diffraction. The crystal belongs to orthorhombic P2(1)2(1)2(1) space group with unit cell parameters a = 6.1840 (12) Å, b = 10.372 (2) Å, c = 25.702 (5) Å, V = 1648.5 (6) Å3, Z = 4, Dc = 1.343 Mg/m3, λ = 0.71073 Å, μ(Mo Kα) = 0.102 mm−1, F(000) = 704. X-ray diffraction analysis reveals that the compound adopts chair-chair conformation. The newly formed γ-lactam moiety is fused to glucopyranoside ring by C2 to form spirosugar. The crystal structure is stabilized by N–H···O2 hydrogen bond. Novel methyl 4,6-O-benzylidene-3-ketoglucopyranosid-fused γ-lactam was synthesized and characterized by HRMS, 1H and 13C-NMR, IR, elemental analysis and single crystal X-ray diffraction.

  标题化合物甲基 4,6-O-亚苄基-3-酮基吡喃葡萄糖苷-熔融 γ-内酰胺是在温和条件下，通过多步反应顺序，从 2-氧代吡喃葡萄糖苷一步合成的。通过 HRMS、1H 和 13C-NMR、IR、元素分析和单晶 X 射线衍射对其进行了表征。该晶体属于正菱形 P2(1)2(1)2(1) 空间群，单胞参数 a = 6.1840 (12) Å, b = 10.372 (2) Å, c = 25.702 (5) Å, V = 1648.5 (6) Å3, Z = 4, Dc = 1.343 Mg/m3, λ = 0.71073 Å, μ(Mo Kα) = 0.102 mm-1, F(000) = 704.X 射线衍射分析表明，该化合物呈椅椅构象。新形成的 γ-内酰胺分子通过 C2 与吡喃葡萄糖苷环融合，形成螺糖。晶体结构由 N-H-O2 氢键稳定。合成了新型 4,6-O-亚苄基-3-酮基吡喃葡萄糖苷融合γ-内酰胺，并通过 HRMS、1H 和 13C-NMR、IR、元素分析和单晶 X 射线衍射对其进行了表征。
• Synthesis of 2,2-Bis-<i>C</i>-functionalized Chain Glucosid-3-ketals
  作者：Fuyi Zhang、Hong Liu、Yingming Sheng、Hongmin Liu

  DOI：10.1002/cjoc.201180431

  日期：2012.1

  synthesized in the form of ketal. The synthesis is rather convenient through one pot multistep reactions and no expensive reagents are involved. The products are formed via autoxidation‐Michael addition mechanism and their structures were characterized by X‐ray crystallographic analysis. Their crystal stuctures are stablilized by intermolecular hydrogen bonds and double‐strand supramolecular stacking is

  以缩酮形式合成了新型的2,2- bis - C-功能化链状葡萄糖苷-3-ulose。通过一锅多步反应，合成非常方便，并且不需要昂贵的试剂。产品通过自氧化迈克尔加成机理形成，其结构通过X射线晶体学分析进行了表征。它们的晶体结构通过分子间氢键稳定，并观察到双链超分子堆叠。
• A novel glycoside lactone derivative with a 2-C-unsaturated diester substituent
  作者：Fuyi Zhang、Chen-Xia Du、Hong-Min Liu、Yu Zhu

  DOI：10.1107/s0108270101015505

  日期：2001.11.15

  The title 4,6-O-benzylidene-alpha -D-glucopyranoside (systematic name: methyl 4-methoxy-2-oxo-8-phenyl-1,2,5a,6,9a,9b-hexahydro-4H,8H-7,9-dioxacyclopenta[c]chromene-3-carboxylate), C18H18O8, has been synthesized from the reaction of methyl 4,6-O-benzylidene-alpha -D-2-ketoglucopyranoside with diethyl or dimethyl malonate. The compound adopts a chair-chair conformation. The newly formed five-membered ring is fused to the glucopyranoside ring along the C-2-C-3 bond and is planar with an r.m.s. deviation of 0.0091 Angstrom.
• Novel synthesis of methyl 4,6-O-benzylidenespiro[2-deoxy-α-d-arabino-hexopyranoside-2,2′-imidazolidine] and its homologue and sugar-γ-butyrolactam derivatives from methyl 4,6-O-benzylidene-α-d-arabino-hexopyranosid-2-ulose
  作者：Fuyi Zhang、Hong Liu、Yong-Feng Li、Hong-Min Liu

  DOI：10.1016/j.carres.2010.01.004

  日期：2010.4

  Novel methyl 4,6-O-benzylidenespiro[2-deoxy-alpha-D-arabino-hexopyranoside-2,2'-imidazolidine] and its homologue methyl 4,6-O-benzylidene-3',4',5',6'-tetrahydro-1'H-spiro[2-deoxy-alpha-D-arabino-hexopyranoside-2,2'-pyrimidine] have been synthesized in good yields by reaction of methyl 4,6-O-benzylidene-alpha-D-arabino-hexopyranosid-2-ulose with 1,2-diaminoethane and 1,3-diaminopropane. The results

  新型甲基4,6-O-亚苄基螺[2-脱氧-α-D-阿拉伯糖基-己吡喃糖苷-2,2'-咪唑烷]及其同系物甲基4,6-O-亚苄基-3'，4'，5'，通过4,6-O-亚苄基-α-甲基的反应以高收率合成了6'-四氢-1'H-螺[2-脱氧-α-D-阿拉伯糖基-己吡喃糖苷-2,2'-嘧啶]具有1，2-二氨基乙烷和1，3-二氨基丙烷的D-阿拉伯糖基己基吡喃糖-2-酮糖。结果完全不同于与芳基胺或烷基胺的反应。一锅合成新型（E）-甲基4- [羟基（甲氧基）亚甲基] -5-氧-1-烷基-（4,6-O-亚苄基-2-脱氧-α-D-吡喃葡萄糖基）[3通过烷基胺与含丁烯内酯的糖的反应获得了1,2-b]吡咯烷，该糖衍生自甲基4的醛醇缩合 带有丙二酸二乙酯的6-O-亚苄基-α-D-阿拉伯糖基-吡喃果糖基-2-ulose。这些糖-γ-丁内酰胺衍生物是潜在的GABA受体配体。