methyl (3R,4S,5R)-3-hydroxy-4,5-<(2S,3S)-2,3-dimethoxybutan-2,3-dioxy>-cyclohex-1-en-1-carboxylate | 245054-32-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (3R,4S,5R)-3-hydroxy-4,5-<(2S,3S)-2,3-dimethoxybutan-2,3-dioxy>-cyclohex-1-en-1-carboxylate
• 英文别名: methyl (1R,3S,4S,6R,7R)-7-hydroxy-3,4-dimethyl-3,4-dimethoxy-2,5-dioxabicyclo[4.4.0]dec-8-ene-9-carboxylate；methyl (3R,4R,5R)-3-hydroxy-4,5-(2,3-dimethoxybutane-2,3-dioxy)-1-cyclohex-1-ene-1-carboxylate；methyl (3R,4S,5R)-3-hydroxy-4,5-(2,3-dimethoxybutan-2,3-dioxy)cyclohex-1-ene-1-carboxylate；methyl (2S,3S,4aR,5R,8aR)-5-hydroxy-2,3-dimethoxy-2,3-dimethyl-4a,5,8,8a-tetrahydro-1,4-benzodioxine-7-carboxylate
• CAS: 245054-32-4
• 化学式: C₁₄H₂₂O₇
• 分子量: 302.324
• InChiKey: QEKVKHCYCSPTAJ-AFCCXKIYSA-N

物化性质

• 沸点：
  407.8±45.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  83.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl (3R,4S,5R)-3-hydroxy-4,5-<(2S,3S)-2,3-dimethoxybutan-2,3-dioxy>-cyclohex-1-en-1-carboxylate 在 水 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以100%的产率得到methyl shikimate
  参考文献：
  名称：

  奎尼酸向sh草酸衍生物的有效转化

  摘要：

  （-）- sh草酸甲酯和（-）-3-表-shi草酸酯和3-氨基shi草酸酯衍生物的合成已经通过短而有效的途径由奎宁酸实现。

  DOI：

  10.1016/s0040-4020(99)00431-7
• 作为产物：
  描述：

  (2'S,3'S)-methyl 3-O-tert-butyl(dimethyl)silyl-4-O,5-O-(2',3'-dimethoxybutane-2',3'-diyl)quinate 在 双[Α,Α-双(三氟甲基)苯甲醇合]二苯硫 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 27.0h， 生成 methyl (3R,4S,5R)-3-hydroxy-4,5-<(2S,3S)-2,3-dimethoxybutan-2,3-dioxy>-cyclohex-1-en-1-carboxylate
  参考文献：
  名称：

  Approaches to the synthesis of 3-fluoroshikimic acids

  摘要：

  Exploitation of the dual dehydrating and fluorodeoxygenating properties of the dialkylaminosulfurtrifluorides has allowed access to the C3-fluorinated analogues of (-)-shikimic acid. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.06.092

文献信息

• A pattern recognition approach to 14-epi-hydrophenanthrene core of the morphine alkaloids based on shikimic acid
  作者：Tung N. Dinh、Anqi Chen、Christina L.L. Chai

  DOI：10.1016/j.tet.2011.03.063

  日期：2011.5

  An expeditious and stereoselective construction of C-14-epimer of the tetracyclic hydrophenanthrene framework of the morphine alkaloids is described. The core structure is obtained in nine steps in 11% overall yield from shikimic acid via three key transformations: (i) coupling of shikimic acid with 2-iodoisovanillin at C-3 by double SN2 inversion to form the aryl ether 5; (ii) an intramolecular Heck

  描述了吗啡生物碱的四环氢菲骨架的C-14-受体的快速和立体选择性构建。通过三个关键的转化，从sh草酸通过九个步骤以11％的总收率获得核心结构：（i）double草酸与2-碘异香兰素在C-3处通过两次S N 2转化形成芳基醚5；（ii）分子内的Heck反应以构建二氢苯并呋喃环，和（iii）McMurry偶合以提供对菲核心。
• Conversion of (−)-3-Dehydroshikimic Acid into Derivatives of the (+)-Enantiomer
  作者：Martin G. Banwell、Alison J. Edwards、Michael Essers、Katrina A. Jolliffe

  DOI：10.1021/jo034689c

  日期：2003.8.1

  (-)-3-DHS (1), a compound available in large quantity through "engineering" of the shikimic acid pathway, has been converted over eight steps into the methyl ester, ent-2, of the (+)-enantiomer. Methyl (+)-shikimate (15) and its C-3 epimer (ent-5) have also been prepared by related means.

  （-）-3-DHS（1）是通过the草酸途径的“工程化”而大量获得的化合物，经八步转化为（+）-对映体的甲酯ent-2。（+）-shi草酸甲酯（15）及其C-3差向异构体（ent-5）也已通过相关方法制备。
• Efficient synthesis of (−)-methyl 3-epi-shikimate and methyl 3-epi-quinate by one-pot selective protection of trans-1,2-diols
  作者：Nuria Armesto、Miguel Ferrero、Susana Fernández、Vicente Gotor

  DOI：10.1016/s0040-4039(00)01507-0

  日期：2000.11

  have been achieved by in situ formation of the protecting group (2,2,3,3-tetramethoxybutane). The synthetic utility of the protected derivatives is demonstrated by the preparation of (−)-methyl 3-epi-shikimate and methyl 3-epi-quinate through a new and efficient route from the parent acids.

  通过原位形成保护基团（2,2,3,3-四甲氧基丁烷）可以实现sh草酸和奎尼酸的反式-1,2-二醇保护。受保护的衍生物的合成效用通过从母体酸通过新的有效途径制备（-）-3- Epi- shikimate甲酯和3- epi- quinate甲酯来证明。
• Efficient syntheses of (−)-shikimate and (−)-quinate 3-phosphate via trans vicinal diol protection with 2,2,3,3-tetramethoxybutane (TMB) of shikimic and quinic acids
  作者：Tzenge-Lien Shih、Shih-Hsiung Wu

  DOI：10.1016/s0040-4039(00)00280-x

  日期：2000.4

  (−)-Shikimate 3-phosphate and (−)-quinate 3-phosphate can be synthesized by selective protection of their trans diol functionality using 2,2,3,3-tetramethoxybutane (TMB) using d-(−)-shikimic acid and d-(−)-quinic acid as starting materials. This versatile reagent facilitates the synthesis of these important biological targets in fewer steps than previously reported. By the proper choice of protecting

  （-）-Shikimate 3-phosphate和（-）-quinate 3-phosphate可通过使用d-（-）-shikimic acid使用2,2,3,3-四甲氧基丁烷（TMB）选择性保护其反式二醇官能团来合成以d-（-）-奎宁酸为原料。与以前报道的相比，这种多功能的试剂以更少的步骤促进了这些重要生物靶标的合成。通过保护基团为C-3羟基在d的适当的选择- （ - ） - （ - ） -莽草酸-3-磷酸奎尼酸，它可以在合成转化为关键中间体。
• A Lemieux–Johnson oxidation of shikimic acid derivatives: facile entry to small library of protected (2S,3S,4R)-2,3,4,7-tetrahydroxy-6-oxoheptanals
  作者：Miroslav Psotka、Miroslava Martinková、Jozef Gonda

  DOI：10.1007/s11696-016-0004-8

  日期：2017.4

  The Lemieux–Johnson oxidation was employed for the cleavage of the carbon–carbon double bond of shikimic acid derivatives. Through this procedure, a series of the sixteen novel (2S,3S,4R)-2,3,4,7-tetrahydroxy-6-oxoheptanals bearing three contiguous stereocentres have been synthesized in excellent yields.

  Lemieux-Johnson氧化法用于裂解iki草酸衍生物的碳-碳双键。通过该程序，已经以优异的产率合成了一系列具有三个连续立体中心的十六种新颖的（2 S，3 S，4 R）-2,3,4,7-四羟基-6-氧庚烷。