methyl (1R,4S,5R)-1-hydroxy-4,5-[(2S,3S)-2,3-dimethoxybutan-2,3-dioxy]-3-oxo-cyclohexan-1-carboxylate | 183474-88-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (1R,4S,5R)-1-hydroxy-4,5-[(2S,3S)-2,3-dimethoxybutan-2,3-dioxy]-3-oxo-cyclohexan-1-carboxylate
• 英文别名: methyl (1S,4S,5R)-1-hydroxy-4,5-<(2S,3S)-2,3-dimethoxybutan-2,3-dioxy>-3-oxo-cyclohexan-1-carboxylate；methyl (1S,3S,4S,6S,9R)-9-hydroxy-3,4-dimethoxy-3,4-dimethyl-7-oxo-2,5-dioxabicyclo[4.4.0]decane-9-carboxylate；methyl (2S,3S,4aR,6R,8aS)-6-hydroxy-2,3-dimethoxy-2,3-dimethyl-8-oxo-4a,5,7,8a-tetrahydrobenzo[b][1,4]dioxine-6-carboxylate
• CAS: 183474-88-6
• 化学式: C₁₄H₂₂O₈
• 分子量: 318.324
• InChiKey: ULQATDCKHCGEFE-JHYOHUSXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl (1R,4S,5R)-1-hydroxy-4,5-[(2S,3S)-2,3-dimethoxybutan-2,3-dioxy]-3-oxo-cyclohexan-1-carboxylate 在 三氟乙酸 作用下， 以 水 为溶剂， 反应 0.25h， 以83%的产率得到methyl 3-dehydroquinate
  参考文献：
  名称：

  A Convenient Method for the Synthesis of Dehydroquinic Acid

  摘要：

  A convenient synthesis of dehydroquinic acid and its corresponding methyl ester are described. Protection of the trans diol of quinic acid, followed by PCC oxidation gave fully protected dehydroquinic acid. This gave methyl dehydroquinate on mild, acid catalyzed hydrolysis. Ester hydrolysis then gave potassium dehydroquinate which was treated with amberlite to afford dehydroquinic acid.

  DOI：

  10.1081/scc-120015805
• 作为产物：
  描述：

  (2S,3S,4aR,6S,8R,8aR)-八氢-6,8-二羟基-2,3-二甲氧基-2,3-二甲基-1,4-苯并二氧杂环己-6-羧酸甲酯 在 ruthenium trichloride 、 potassium metaperiodate 、 potassium carbonate 作用下， 以 氯仿 为溶剂， 反应 48.0h， 生成 methyl (1R,4S,5R)-1-hydroxy-4,5-[(2S,3S)-2,3-dimethoxybutan-2,3-dioxy]-3-oxo-cyclohexan-1-carboxylate
  参考文献：
  名称：

  氟乙烯作为烯醇酸阴离子的等电子替代物：抑制II型脱氢喹啉酶。

  摘要：

  由II型脱氢喹啉酶催化的反应中中间体的氟乙烯类似物是由（-）-奎宁酸经7个步骤合成的，显示是有效的酶抑制剂。

  DOI：

  10.1039/b205105m

文献信息

• Inhibitor Ionization as a Determinant of Binding to 3-Dehydroquinate Synthase
  作者：Feng Tian、Jean-Luc Montchamp、J. W. Frost

  DOI：10.1021/jo960709h

  日期：1996.1.1

  phosphorylmethyl, phosphonoethyl, and phosphonomethyl groups in carbocyclic inhibitors of DHQ synthase. All but one of the carbocyclic inhibitors were synthesized via intermediacy of a 2,3-butane bisacetal-protected 3-dehydroquinic acid. Carbaphosphinate (K(i) = 20 x 10(-)(6) M) was a modest competitive inhibitor of DHQ synthase, while carbaacetate was a linear mixed-type inhibitor (K(i) = 3 x 10(-)(6) M, K(i)'

  在DHQ合酶的碳环抑制剂中，膦酰基甲基和羧甲基一元酸与琥珀酰基，丙二酰基醚，丙二酰基和羟基丙二酰基二酸一起被磷酰基甲基，膦酰基乙基和膦酰基甲基取代。除一种碳环抑制剂外，所有化合物均通过2，3-丁烷双缩醛保护的3-脱氢奎尼酸的中间体合成。氨基膦酸酯（K（i）= 20 x 10（-）（6）M）是DHQ合酶的中等竞争性抑制剂，而氨基甲酸酯则是线性混合型抑制剂（K（i）= 3 x 10（-）（6） ）M，K（i）'= 20 x 10（-）（6）M）。氨基甲酸酯（K（i）= 5 x 10（-）（6）M），氨基甲酸酯醚（K（i）= 7 x 10（-）（6）M），氨基甲酸酯（K（i）= 0.7 x 10（ -）（6）M）和氨基甲酸丙二酸酯（K（i）= 0.3 x 10（-）（6）M）均为竞争性抑制剂。氨基甲酸酯是唯一未被DHQ合酶氧化的抑制剂。
• First diastereoselective synthesis of methyl caffeoyl- and feruloyl-muco-quinates
  作者：Rakesh Jaiswal、Michael H. Dickman、Nikolai Kuhnert

  DOI：10.1039/c2ob25124h

  日期：——

  We report on a diastereoselective synthesis of six derivatives of caffeoyl- and feruloyl-muco-quinic acids. All the muco-quinic acid derivatives were obtained in excellent yield in five steps starting from quinic acid, caffeic acid and ferulic acid. Allyl ether protection of trans-hydroxy cinnamic acids was here introduced to chlorogenic acids synthesis. We show that muco-quinic acid derivatives, which are formally diastereoisomers of chlorogenic acids, can be readily distinguished by their tandem mass spectra

  我们报告了一种非对映选择性合成咖啡酰基和阿魏酰基粘喹酸六种衍生物的方法。以奎宁酸、咖啡酸和阿魏酸为起点，通过五个步骤获得了所有的黏稠奎宁酸衍生物，收率极高。这里将反式羟基肉桂酸的烯丙基醚保护引入到绿原酸合成中。我们的研究表明，作为绿原酸非对映异构体的粘液喹酸衍生物可以通过串联质谱很容易地区分出来。
• (1R,4S,5R)-3-Fluoro-1,4,5-trihydroxy-2-cyclohexene-1-carboxylic acid: the fluoro analogue of the enolate intermediate in the reaction catalyzed by type II dehydroquinases
  作者：Martyn Frederickson、Aleksander W. Roszak、John R. Coggins、Adrian J. Lapthorn、Chris Abell

  DOI：10.1039/b404535a

  日期：——

  The fluoro analogue of the enolate intermediate in the reaction catalyzed by type II dehydroquinases has been prepared from naturally occurring (-)-quinic acid over seven steps and has been shown to be the most potent inhibitor reported to date of the type II enzyme from Mycobacterium tuberculosis.

  由II型脱氢喹啉酶催化的反应中烯醇盐中间体的氟类似物是由天然存在的（-）-奎宁酸经七个步骤制备的，已被证明是迄今为止报道的分枝杆菌II型酶最有效的抑制剂。结核。
• Design, synthesis and evaluation of bifunctional inhibitors of type II dehydroquinase
  作者：Miguel D. Toscano、Martyn Frederickson、David P. Evans、John R. Coggins、Chris Abell、Concepción González-Bello

  DOI：10.1039/b301731a

  日期：——

  quinic acid, and were assayed against type I (Salmonella typhi) and type II (S. coelicolor) dehydroquinases. None of the analogues showed inhibition for type I dehydroquinase. Six of the analogues were shown to have inhibition constants in the micromolar to low millimolar range against the S. coelicolor type II dehydroquinase, while two showed no inhibition. The binding modes of the analogues in the active

  II型脱氢喹啉酶的抑制剂被设计为跨越晶体学研究中为抑制剂（1S，3R，4R）-1,3,4-三羟基-5-环己烯-1-羧酸和甘油分子确定的两个不同的结合位点链霉菌天蓝色的酶。设计了许多化合物以结合两个配体的特征。这些类似物是由奎宁酸合成的，并针对I型（鼠伤寒沙门氏菌）和II型（天蓝色链霉菌）脱氢喹啉酶进行了分析。没有类似物显示出对I型脱氢喹啉酶的抑制。已显示六个类似物在微摩尔至低毫摩尔范围内对S. coelicolor II型脱氢喹啉酶具有抑制常数，而两个没有显示抑制作用。S的活性位点中类似物的结合模式。通过与GOLD1.2分子对接研究了coelicolor酶。这些研究表明了一种结合模式，其中环的晶体结构与（1S，3R，4R）-1,3,4-三羟基-5-环己烯-1-羧酸相似，并且侧链占据了一部分甘油结合口袋。
• 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。