methyl 1-hydroxy-2-oxo-1-cycloheptanecarboxylate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 1-hydroxy-2-oxo-1-cycloheptanecarboxylate
• 英文别名: methyl 1-hydroxy-2-oxo-cycloheptanecarboxylate；methyl 1-hydroxy-2-oxocycloheptanecarboxylate；methyl 2-hydroxycycloheptanone-2-carboxylate；ethyl 2-hydroxycyclohepanone-2-carboxylate；Methyl 1-hydroxy-2-oxocycloheptane-1-carboxylate
• 化学式: C₉H₁₄O₄
• 分子量: 186.208
• InChiKey: KGZFJXHCDSGOHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 1-hydroxy-2-oxo-1-cycloheptanecarboxylate 在 吡啶 、 2,5-二甲基吡啶 、 N,N′-双(对甲苯磺酰)肼 、 四氯化锡 、 二异丁基氢化铝 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 cesium fluoride 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 14.17h， 生成 4-oxacycloundecyne-3,6-dione
  参考文献：
  名称：

  Fragmentation of Bicyclic γ-Silyloxy-β-hydroxy-α-diazolactones as an Approach to Ynolides

  摘要：

  Medium-sized ynolides were prepared by the Lewis acid-mediated fragmentation of bicyclic gamma-silyloxy-beta-hydroxy-alpha-diazolactones in which the C beta-C gamma bond is the ring fusion bond. Although these lactone fragmentation substrates reacted somewhat less efficiently than their carbocyclic counterparts, the fragmentation provided 11-membered ynolides in up to 84% yield. Unlike prior fragmentations of similar substrates, elevated temperatures were required to obtain optimum yields of the ynolide products. The ynolides reported herein have ring sizes of 10 or 11, which are the smallest reported to date.

  DOI：

  10.1021/jo500634d
• 作为产物：
  描述：

  2-氧代-1-环庚烷甲酸甲酯 在 cerium(III) chloride 、 氧气 作用下， 以 异丙醇 为溶剂， 反应 16.0h， 以96%的产率得到methyl 1-hydroxy-2-oxo-1-cycloheptanecarboxylate
  参考文献：
  名称：

  铈催化 β-二羰基化合物与分子氧的 α-氧化

  摘要：

  β-酮酯和β-二酮在作为溶剂的 i-PrOH 中，在 5 mol% CeCl 3 .7 H 2 O 存在下被分子氧α-羟基化。该方法仅限于具有 α-烷基取代基的底物。使用环状起始材料可实现最佳产率。

  DOI：

  10.1055/s-2002-19331

文献信息

• A Simple and Effective Method for α-Hydroxylation of β-Dicarbonyl Compounds Using Oxone as an Oxidant without a Catalyst
  作者：Jun Yu、Jian Cui、Chi Zhang

  DOI：10.1002/ejoc.201000940

  日期：2010.12

  Oxone has been found to be a highly efficient reagent for the introduction of a hydroxy group at the α position of a variety of β-dicarbonyl compounds in the homogeneous solvent mixture of water and 1,4-dioxane at 60 °C.

  已发现 Oxone 是一种高效试剂，可在 60 °C 下在水和 1,4-二恶烷的均相溶剂混合物中在各种 β-二羰基化合物的 α 位引入羟基。
• Cerium-catalyzed α-Oxidation of β-Dicarbonyl Compounds with Molecular Oxygen
  作者：Jens Christoffers、Thomas Werner

  DOI：10.1055/s-2002-19331

  日期：——

  β-Ketoesters and β-diketones are α-hydroxylated by molecular oxygen in the presence of 5 mol% CeCl 3 .7 H 2 O in i-PrOH as solvent. The method is limited to substrates with an α-alkyl substituent. Optimal yields are achieved with cyclic starting materials.

  β-酮酯和β-二酮在作为溶剂的 i-PrOH 中，在 5 mol% CeCl 3 .7 H 2 O 存在下被分子氧α-羟基化。该方法仅限于具有 α-烷基取代基的底物。使用环状起始材料可实现最佳产率。
• Preparation of Acyloins by Cerium-Catalyzed, Direct Hydroxylation ofβ-Dicarbonyl Compounds with Molecular Oxygen
  作者：Jens Christoffers、Thomas Werner、Sven Unger、Wolfgang Frey

  DOI：10.1002/ejoc.200390075

  日期：2003.2

  We report the metal-catalyzed α-hydroxylation of a variety of cyclic and acyclic β-dicarbonyl compounds by molecular oxygen. The decisive advantage of this new method is the use of catalytic amounts of the nontoxic cerium salt CeCl3·7H2O in 2-propanol at ambient temperature. Most of the cyclic substrates 4a−4i give high yields of analytically pure products 5a−5i, and the workup procedure is simple

  我们报告了金属催化的分子氧对各种环状和非环状 β-二羰基化合物的 α-羟基化。这种新方法的决定性优势是在环境温度下在 2-丙醇中使用催化量的无毒铈盐 CeCl3·7H2O。大多数环状底物 4a-4i 产生高产率的分析纯产物 5a-5i，后处理程序是通过硅胶简单过滤。然而，无环二羰基化合物 4j-4p 的氧化伴随着副反应和分解，显着降低了产物 5j-5p 的产率。提出的机制与实验结果一致，特别是观察到的氧摄取。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Cerium-Catalyzed Reaction ofβ-Dicarbonyl Compounds with Styrene and Atmospheric Oxygen
  作者：Jens Christoffers、Thomas Werner、Wolfgang Frey、Angelika Baro

  DOI：10.1002/ejoc.200300439

  日期：2003.12

  The cerium-catalyzed C−C coupling reaction of carbo- and heterocyclic β-dicarbonyl compounds 1 with styrenes 4, using oxygen (air) as the oxidant, at ambient temperature, is reported. The reaction afforded a mixture of diastereoisomeric hydroperoxides 5 which could be transformed into the unique dioxo compounds 6 by disproportionation of the peroxo function under treatment with acetyl chloride/pyridine

  据报道，使用氧气（空气）作为氧化剂，在环境温度下，铈催化的碳和杂环 β-二羰基化合物 1 与苯乙烯 4 的 C-C 偶联反应。该反应提供了非对映异构氢过氧化物 5 的混合物，其可以通过在乙酰氯/吡啶处理下使过氧官能团歧化而转化为独特的二氧代化合物 6。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Iron-catalyzed hydroxylation of β-ketoesters with hydrogen peroxide as oxidant
  作者：Dongmei Li、Kristin Schröder、Bianca Bitterlich、Man Kin Tse、Matthias Beller

  DOI：10.1016/j.tetlet.2008.07.157

  日期：2008.10

  The hydroxylation of β-ketoesters was studied using simple iron catalysts and 30 wt % hydrogen peroxide as the terminal oxidant. The highest activity and yield were achieved in the presence of iron(III) chloride. Cyclic β-ketoesters could be smoothly hydroxylated in 75–90% yield. For linear β-ketoester and β-ketoamide, the chloro-substituted products were obtained.

  使用简单的铁催化剂和30 wt％的过氧化氢作为末端氧化剂，研究了β-酮酸酯的羟基化作用。在氯化铁（III）的存在下获得了最高的活性和收率。环状β-酮酸酯可以75-90％的收率平稳地被羟基化。对于线性β-酮酸酯和β-酮酰胺，获得了氯取代的产物。