methyl 1-hydroxy-2-oxocyclopentane carboxylate | 151930-48-2

• 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-oxocyclopentane carboxylate
• 英文别名: Methyl 1-hydroxy-2-oxocyclopentane-1-carboxylate
• CAS: 151930-48-2
• 化学式: C₇H₁₀O₄
• 分子量: 158.154
• InChiKey: HEEQREGJKAZYPP-UHFFFAOYSA-N

物化性质

• 沸点：
  244.9±40.0 °C(Predicted)
• 密度：
  1.337±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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-oxocyclopentane carboxylate 在 水 、 magnesium iodide 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以42%的产率得到2-(1,2-Dihydroxycyclopentyl)oxycyclopentan-1-one
  参考文献：
  名称：

  Lewis acid-promoted α-hydroxy β-dicarbonyl to α-ketol ester rearrangement

  摘要：

  The decarbomethoxylation reaction of a substituted alpha-hydroxy-alpha-carbomethoxy pentacyclic substituted ketone, used as an advanced intermediate in the synthesis of the alkaloid aspidophytine, can be effected by heating with MgI2 in CH3CN. The reaction was shown to proceed by a novel a-hydroxy beta-dicarbonyl to alpha-ketol ester rearrangement. It was possible to isolate a carbonate intermediate in 75% yield, thereby providing support for the proposed pathway. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.09.071
• 作为产物：
  描述：

  2-甲氧羰基环戊酮 在 iron(III) chloride 、 双氧水 作用下， 以 2-甲基-2-丁醇 、 水 为溶剂， 反应 6.0h， 以84%的产率得到methyl 1-hydroxy-2-oxocyclopentane carboxylate
  参考文献：
  名称：

  铁以过氧化氢为氧化剂催化β-酮酸酯的羟基化

  摘要：

  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。

  DOI：

  10.1016/j.tetlet.2008.07.157

文献信息

• Magnesium Monoperphthalate (MMPP): a Convenient Oxidant for the Direct Rubottom Oxidation of Malonates, β‐Keto Esters, and Amides
  作者：Sara Meninno、Rosaria Villano、Alessandra Lattanzi

  DOI：10.1002/ejoc.202100098

  日期：2021.3.19

  Commercially available and inexpensive magnesium monoperphthalate (MMPP) was found to be an effective oxidant for the first direct Rubottom hydroxylation of α‐substituted malonates, β‐ketoesters, and β‐ketoamides, when working in ethanol at room temperature and using NaHCO3 as basic additive. The feasibility of gram scale oxidation was also demonstrated.

  当在室温下在乙醇中工作并且使用NaHCO 3作为碱性溶液时，发现市售廉价的单过苯甲酸镁（MMPP）是α-取代的丙二酸酯，β-酮酸酯和β-酮酰胺的首次直接Rubottom羟基化的有效氧化剂。添加剂。还证明了克级氧化的可行性。
• 1,5,7‐Triazabicyclo[4.4.0]dec‐5‐ene Enhances Activity of Peroxide Intermediates in Phosphine‐Free α‐Hydroxylation of Ketones
  作者：Yongtao Wang、Rui Lu、Jia Yao、Haoran Li

  DOI：10.1002/anie.202014478

  日期：2021.3.15

  The critical role of double hydrogen bonds was addressed for the aerobic α‐hydroxylation of ketones catalyzed by 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD), in the absence of either a metal catalyst or phosphine reductant. Experimental and theoretical investigations were performed to study the mechanism. In addition to initiating the reaction by proton abstraction, a more important role of TBD was revealed

  在没有金属催化剂或磷化氢的情况下，双氢键的关键作用已被1,5,7-三氮杂双环[4.4.0] dec-5-烯（TBD）催化的酮的好氧α-羟基化反应还原剂。进行了实验和理论研究以研究其机理。除了通过质子提取引发反应之外，还显示了TBD的更重要作用，即增强过氧化物中间体的氧化能力，从而允许使用DMSO而不是常用的膦还原剂。核Overhauser效应光谱（NOESY）的进一步表征证实了TBD和酮之间存在双氢键，动力学研究表明，TBD-烯醇加合物上的双氧攻击是决定速率的步骤。
• Synthesis of Tetrasubstituted Furan Derivatives by Condensation of 1,3-Diketones with Cyclic α-Hydroxy-β-oxo Esters
  作者：Barhiem Schickmous、Jens Christoffers

  DOI：10.1002/ejoc.201402388

  日期：2014.7

  alicyclic and heterocyclic α-hydroxy-β-oxo esters under acidic conditions [0.1 equiv. cerium(III) salt in AcOH]. With [b]-annulated 4-acyl-3-hydroxy-5-methylfuran-2-carboxylates as common intermediates, the reaction proceeded along different pathways depending on the starting materials used: Alicyclic α-hydroxy-β-oxo esters gave cycloalkane-annulated furans as products. The ester group was lost after

  四取代的 3-酰基呋喃衍生物是通过乙酰丙酮与脂环和杂环 α-羟基-β-氧代酯在酸性条件下缩合获得的 [0.1 当量。AcOH 中的铈 (III) 盐]。[b]-环化 4-acyl-3-hydroxy-5-methylfuran-2-carboxylates 作为常见的中间体，反应沿着不同的途径进行，具体取决于所用的起始原料：脂环族 α-羟基-β-氧代酯得到环烷烃-作为产品的环化呋喃。在高温下皂化和脱羧后酯基丢失。当以四氢噻喃酮衍生物为原料时，得到了噻吩并[3,4-b]-环化的 2H-呋喃。以哌啶酮或四氢吡喃酮为起始原料，杂环六元环在逆曼尼希型反应中裂解，失去一个碳原子。
• HYDROXYLATION OF BETA-DICARBONYLS WITH ZIRCONIUM CATALYSTS
  申请人：CASALNUOVO ALBERT LOREN

  公开号：US20080306259A1

  公开（公告）日：2008-12-11

  The present invention pertains to a process for preparing a compound of Formula I that is achiral, racemic or enantiomerically enriched at the hydroxylation center indicated by * comprising contacting a compound of Formula II with an oxidant selected from oxygen, hydrogen peroxide, peracids or alkyl hydropetoxides in the presence of a zirconium complex, wherein R 1 , R 2 and R 3 are as defined in the disclosure. This invention also pertains to zirconium complexes useful in this procedure comprising zirconium and a ligand of Formula III or its enantiomer wherein J, R 6 and n are as defined in the disclosure. This invention further pertains to a compound of Formula III or its enantiomer.

  本发明涉及一种制备公式I化合物的方法，该化合物是在羟基化中心处无手性、外消旋或对映富集的，所述方法包括将公式II化合物与氧、过氧化氢、过酸或烷基过氧化物等氧化剂在锆配合物的存在下接触，其中R1、R2和R3如本文所定义。本发明还涉及在该过程中有用的锆配合物，其包括锆和公式III配体或其对映体，其中J、R6和n如本文所定义。本发明还涉及公式III或其对映体的化合物。
• Hydroxylation of Beta-Dicarbonyls with Zirconium Catalysts
  申请人：Casalnuovo Albert Loren

  公开号：US20100185014A1

  公开（公告）日：2010-07-22

  The present invention pertains to a process for preparing a compound of Formula I that is achiral, racemic or enantiomerically enriched at the hydroxylation center indicated by * comprising contacting a compound of Formula II with an oxidant selected from oxygen, hydrogen peroxide, peracids or alkyl hydroperoxides in the presence of a zirconium complex, wherein R 1 , R 2 and R 3 are as defined in the disclosure. This invention also pertains to zirconium complexes useful in this procedure comprising zirconium and a ligand of Formula III or its enantiomer wherein J, R 6 and n are as defined in the disclosure. This invention further pertains to a compound of Formula III or its enantiomer.

  本发明涉及一种制备公式I化合物的方法，该化合物是在*处的羟基化中心上是无手性、外消旋或对映富集的，包括将公式II化合物与氧气、过氧化氢、过酸或烷基过氧化物等氧化剂在锆配合物存在下接触，其中R1、R2和R3如本文所定义。本发明还涉及在该过程中有用的锆配合物，包括锆和公式III或其对映体的配体，其中J、R6和n如本文所定义。本发明还涉及公式III或其对映体的化合物。