methyl 4,6-O-benzylidene-3-deoxy-2-O-(4-methoxybenzyl)-α-D-arabinopyranoside | 226885-87-6

• 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-3-deoxy-2-O-(4-methoxybenzyl)-α-D-arabinopyranoside
• 英文别名: (2R,4aR,6S,7S,8aS)-6-methoxy-7-[(4-methoxyphenyl)methoxy]-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine
• CAS: 226885-87-6
• 化学式: C₂₂H₂₆O₆
• 分子量: 386.445
• InChiKey: WHMHGCKJZPSAKQ-ITBHCLRTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 4,6-O-benzylidene-3-deoxy-2-O-(4-methoxybenzyl)-α-D-arabinopyranoside 在 吡啶 、 咪唑 、 potassium tert-butylate 、 水 、 碘 、 mercury(II) trifluoroacetate 、 溶剂黄146 、 甲基磺酰氯 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 N,N-二异丙基乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 丙酮 、 甲苯 为溶剂， 生成 (diethoxy-phosphoryl)-acetic acid 5-(4-methoxy-benzyloxy)-2-oxo-cyclohex-3-enyl ester
  参考文献：
  名称：

  Enantioselective synthesis of phyllanthurinolactone, a leaf-closing substance of Phyllanthus urinaria L., and its analogs toward the development of molecular probes

  摘要：

  We report enantioselective synthesis of phyllanthurinolactone (1), a leaf-closing substance of Phyllanthus urinaria L., and its analogs with sugars other than D-glucose. Structure-activity relationship study using them revealed that the structure of the sugar moiety did not affect their bioactivity at all. This result is very important for the development of molecular probes based on the structure of 1. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.05.129
• 作为产物：
  描述：

  methyl 2,3-anhydro-4,6-O-benzilidene-α-D-mannopyranoside 在 lithium aluminium tetrahydride 、 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 生成 methyl 4,6-O-benzylidene-3-deoxy-2-O-(4-methoxybenzyl)-α-D-arabinopyranoside
  参考文献：
  名称：

  Enantioselective synthesis of phyllanthurinolactone, a leaf-closing substance of Phyllanthus urinaria L., and its analogs toward the development of molecular probes

  摘要：

  We report enantioselective synthesis of phyllanthurinolactone (1), a leaf-closing substance of Phyllanthus urinaria L., and its analogs with sugars other than D-glucose. Structure-activity relationship study using them revealed that the structure of the sugar moiety did not affect their bioactivity at all. This result is very important for the development of molecular probes based on the structure of 1. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.05.129

文献信息

• Total synthesis of paniculide A from d-glucose
  作者：Seiji Amano、Noriaki Takemura、Masami Ohtsuka、Seiichiro Ogawa、Noritaka Chida

  DOI：10.1016/s0040-4020(99)00096-4

  日期：1999.3

  chiral total synthesis of paniculide A (1), a highly oxygenated sesquiterpene possessing a bisabolane skeleton, starting from D-glucose is described. The two different approaches, both involved Ferrier's carbocyclization reaction to construct the cyclohexane unit in 1, were explored. The first approach, employing the carbocyclization of bicyclic substrate furnished the formal total synthesis. The second

  描述了以D-葡萄糖为原料的手性全合成Paniculide A（1），它是一种具有双水硼烷骨架的高度氧化的倍半萜烯。探索了两种不同的方法，均涉及Ferrier的碳环化反应以构建1中的环己烷单元。采用双环底物的碳环化的第一种方法提供了正式的全合成。第二种方法旨在抑制在第一种方法中观察到的不良副反应，该方法采用了单环底物的碳环化和克莱森重排以形成立体选择性碳-碳键。成功全合成1 揭示了Ferrier的碳环化和Claisen重排相结合对于具有环己烷单元的高度氧化的天然产物的手性合成的有效性。
• <i>β</i> -Mannosylation through <i>O</i> -Alkylation of Anomeric Cesium Alkoxides: Mechanistic Studies and Synthesis of the Hexasaccharide Core of Complex Fucosylated N-Linked Glycans
  作者：Shuai Meng、Bishwa Raj Bhetuwal、Hai Nguyen、Xiaotian Qi、Cheng Fang、Kevin Saybolt、Xiaohua Li、Peng Liu、Jianglong Zhu

  DOI：10.1002/ejoc.202000313

  日期：2020.4.23

  analysis suggested that monomeric cesium alkoxides be the key reactive species for alkylation with electrophiles. DFT calculations supported that oxygen atoms at C2, C3, and C6 of mannose promote the deprotonation of the anomeric hydroxyl group by Cs2CO3 and chelating interactions between Cs and these oxygen atoms favour the formation of equatorial anomeric alkoxides, leading to the highly β-selective anomeric

  许多结构不同的 D-甘露糖衍生的内醇，包括各种脱氧-D-甘露糖和构象受限的双环 D-甘露糖，已被合成并在通过 Cs2CO3 介导的异头 O-烷基化的 β-甘露糖基化机理研究中进行了研究。发现脱氧甘露糖或构象受限的双环 D-甘露糖不如它们相应的母体甘露糖具有反应性。当 C2-OH 处于游离状态时，这种类型的 β-甘露糖基化会有效地进行，保护它会导致较差的结果。D-甘露糖衍生的异头铯醇盐的 NMR 研究表明去质子化后赤道 β-异头物占优势。反应进程动力学分析表明单体铯醇盐是与亲电试剂烷基化的关键反应物种。DFT 计算支持甘露糖 C2、C3 和 C6 处的氧原子促进 Cs2CO3 对异头羟基的去质子化，并且 Cs 和这些氧原子之间的螯合相互作用有利于形成赤道异头醇盐，导致高度 β 选择性异头O-烷基化。基于实验数据和计算结果，提出了这种β-甘露糖基化的修正机制。复杂岩藻糖基化 N-连接聚糖的六糖核心的有效合成证明了这种
• Enantioselective synthesis of phyllanthurinolactone, a leaf-closing substance of Phyllanthus urinaria L., and its analogs toward the development of molecular probes
  作者：Yoshifumi Urakawa、Takanori Sugimoto、Hirotaka Sato、Minoru Ueda

  DOI：10.1016/j.tetlet.2004.05.129

  日期：2004.7

  We report enantioselective synthesis of phyllanthurinolactone (1), a leaf-closing substance of Phyllanthus urinaria L., and its analogs with sugars other than D-glucose. Structure-activity relationship study using them revealed that the structure of the sugar moiety did not affect their bioactivity at all. This result is very important for the development of molecular probes based on the structure of 1. (C) 2004 Elsevier Ltd. All rights reserved.