cyclopent-2-enyl 4-methoxybenzoate | 137919-07-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: cyclopent-2-enyl 4-methoxybenzoate
• 英文别名: Cyclopent-2-en-1-yl 4-methoxybenzoate；cyclopent-2-en-1-yl 4-methoxybenzoate
• CAS: 137919-07-4
• 化学式: C₁₃H₁₄O₃
• 分子量: 218.252
• InChiKey: DWFQRDPKCUDLOC-UHFFFAOYSA-N

物化性质

• 沸点：
  331.4±35.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  cyclopent-2-enyl 4-methoxybenzoate 在 臭氧 作用下， 以 二氯甲烷 为溶剂， 生成 endo-2-<(4-methoxybenzoyl)oxy>-6,7,8-trioxabicyclo<3.2.1>octane 、 exo-2-<(4-methoxybenzoyl)oxy>-6,7,8-trioxabicyclo<3.2.1>octane
  参考文献：
  名称：

  The influence of remote heteroatom substituents on the stereoselectivity of cyclopentene ozonolysis

  摘要：

  The stereoselectivity for ozonide formation from cyclopentenes with allylic heteroatom substituents has been examined. Silyl ethers give high selectivity in favor of the exo-substituted ozonide, while esters of 2-cyclopentenol form ozonide mixtures with little stereoselection. Trapping experiments establish that fragmentation of the primary ozonides is highly regioselective to give only one of the isomeric omega-oxo carbonyl oxide intermediates and that the variation in final ozonide stereochemistry results from differing interactions between the remote substituent groups and the carbonyl oxide system during cyclization of this intermediate. The effect of substituent and solvent on ozonide stereochemistry suggests a dominant role for electrostatic repulsion between carbonyl oxide and the heteroatom substituent during intramolecular cycloaddition. A chair-like transition state is proposed for this process and is in accord with the increase in exo selectivity for derivatives of 2-methyl-2-cyclopentenol.

  DOI：

  10.1021/jo00028a059
• 作为产物：
  描述：

  大茴香酸 、 环戊烯 在 叔丁基过氧化氢 作用下， 以 水 、 乙腈 为溶剂， 反应 24.0h， 以84%的产率得到cyclopent-2-enyl 4-methoxybenzoate
  参考文献：
  名称：

  铜铝混合氧化物催化烯烃的烯丙基氧化

  摘要：

  提出了一种以铜铝混合氧化物为催化剂的环状烯烃的烯丙基氧化策略。该反应包括使用叔丁基氢过氧化物作为氧化剂用羧酸处理烯烃。在所有情况下，均获得相应的烯丙基酯。当使用1-脯氨酸时，获得烯丙基醇或酮。环己烯和瓦伦烯的氧化已通过实验设计（DoE）统计方法进行了优化。

  DOI：

  10.1021/ol500198c

文献信息

• Copper-catalyzed oxidative coupling of acids with alkanes involving dehydrogenation: facile access to allylic esters and alkylalkenes
  作者：Cheng-Yong Wang、Ren-Jie Song、Wen-Ting Wei、Jian-Hong Fan、Jin-Heng Li

  DOI：10.1039/c4cc09393c

  日期：——

  We here describe a new copper-catalyzed oxidative coupling of acids with alkanes for the selective synthesis of allylic esters and alkylalkenes. This method achieves multiple dehydrogenation and esterification, representing a new unactivated C(sp(3))-H oxidative esterification of acids with common alkanes.

  我们在这里描述了一种新的铜催化的酸与烷烃的氧化偶联反应，用于选择性合成烯丙基酯和烷基烯烃。此方法实现多次脱氢和酯化反应，代表酸与普通烷烃的新的未活化的C（sp（3））-H氧化酯化反应。
• Copper porphyrin as efficient catalysts for esterification of allyl sp3 C H bond with carboxylic acid
  作者：Ming-Feng Xiong、Atif Ali、Waseem Akram、Hao Zhang、Li-Ping Si、Hai-Yang Liu

  DOI：10.1016/j.catcom.2019.04.001

  日期：2019.5

  We described that copper 5,10,15,20-tetrakis (ethoxycarbonyl)porphyrin (TECP) catalyzed oxidative cross dehydrogenative coupling of allyl sp3 CH bond with acid for the synthesis of allyl esters in a homogeneous system. This reaction proceeded with broad substrate scope and good functional group tolerance. In the gram-level test, the turnover number (TON) reached to 8100 at 0.01 mol% catalyst loading

  我们描述了5,10,15,20-四（乙氧基羰基）卟啉铜（TECP）催化烯丙基sp 3 C H键与酸的氧化交叉脱氢偶联，用于在均相系统中合成烯丙基酯。该反应在宽的底物范围和良好的官能团耐受性下进行。在克级测试中，在催化剂负载量为0.01 mol％时，周转率（TON）达到8100，产率为81％。
• Copper Porphyrin Catalyzed C(sp3)–H Activation via Cross-Dehydrogenative Coupling: Facile Transformation of Aldehydes to Esters
  作者：Hai-Yang Liu、Gao-Qing Yuan、Zi-Wei Shan、Xiao-Yan Chen、Hao Zhang

  DOI：10.1055/a-1813-4235

  日期：2022.7

  catalyzed alkane C–H bond functionalization with aldehydes via cross-dehydrogenative coupling (CDC) using DTBP oxidant has been firstly described in nonsolvents or nonadditives system. Different aryl/heteroaryl carboxylic esters were obtained in good to excellent yields depending on the aldehyde derivatives. This CDC reaction catalyzed by copper porphyrin has the advantages of shorter reaction time, lower reaction

  铜卟啉通过使用 DTBP 氧化剂的交叉脱氢偶联 (CDC) 催化烷烃 C-H 键功能化与醛类首次在非溶剂或非添加剂体系中得到描述。取决于醛衍生物，以良好至优异的产率获得了不同的芳基/杂芳基羧酸酯。这种铜卟啉催化的CDC反应具有反应时间短、反应温度低、催化剂负载量小、反应气氛好氧等优点。
• The influence of remote heteroatom substituents on the stereoselectivity of cyclopentene ozonolysis
  作者：William H. Bunnelle、Terry A. Isbell

  DOI：10.1021/jo00028a059

  日期：1992.1

  The stereoselectivity for ozonide formation from cyclopentenes with allylic heteroatom substituents has been examined. Silyl ethers give high selectivity in favor of the exo-substituted ozonide, while esters of 2-cyclopentenol form ozonide mixtures with little stereoselection. Trapping experiments establish that fragmentation of the primary ozonides is highly regioselective to give only one of the isomeric omega-oxo carbonyl oxide intermediates and that the variation in final ozonide stereochemistry results from differing interactions between the remote substituent groups and the carbonyl oxide system during cyclization of this intermediate. The effect of substituent and solvent on ozonide stereochemistry suggests a dominant role for electrostatic repulsion between carbonyl oxide and the heteroatom substituent during intramolecular cycloaddition. A chair-like transition state is proposed for this process and is in accord with the increase in exo selectivity for derivatives of 2-methyl-2-cyclopentenol.
• Allylic Oxidation of Alkenes Catalyzed by a Copper–Aluminum Mixed Oxide
  作者：Ana Leticia García-Cabeza、Rubén Marín-Barrios、F. Javier Moreno-Dorado、María J. Ortega、Guillermo M. Massanet、Francisco M. Guerra

  DOI：10.1021/ol500198c

  日期：2014.3.21

  strategy for the allylic oxidation of cyclic alkenes with a copper–aluminum mixed oxide as catalyst is presented. The reaction involves the treatment of an alkene with a carboxylic acid employing tert-butyl hydroperoxide as the oxidant. In all cases, the corresponding allylic esters are obtained. When l-proline is employed, the allylic alcohol or ketone is obtained. The oxidation of cyclohexene and

  提出了一种以铜铝混合氧化物为催化剂的环状烯烃的烯丙基氧化策略。该反应包括使用叔丁基氢过氧化物作为氧化剂用羧酸处理烯烃。在所有情况下，均获得相应的烯丙基酯。当使用1-脯氨酸时，获得烯丙基醇或酮。环己烯和瓦伦烯的氧化已通过实验设计（DoE）统计方法进行了优化。