甲基1-乙酰基环戊烷羧酸酯 | 171924-94-0

• 物质功能分类: 化学试剂 - 有机试剂 - 酯类
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 中文名称: 甲基1-乙酰基环戊烷羧酸酯
• 中文别名: 3-乙酰基环戊基甲酸甲酯
• 英文名称: 1-acetyl-1-carbomethoxycyclopentane
• 英文别名: methyl 1-acetylcyclopentanecarboxylate；methyl 1-acetylcyclopentane-1-carboxylate
• CAS: 171924-94-0
• 化学式: C₉H₁₄O₃
• 分子量: 170.208
• InChiKey: LNBQBXOKRKWVLJ-UHFFFAOYSA-N

物化性质

• 沸点：
  228.7±23.0 °C(Predicted)
• 密度：
  1.091±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  甲基1-乙酰基环戊烷羧酸酯 在 rhodium(II) acetate dimer 氢氧化钾 、 三乙胺 、 氯甲酸甲酯 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 dimethyl 6,9-epoxy-6-methyl-10-oxospiro<4,5>decane-7,8-dicarboxylate
  参考文献：
  名称：

  Generation and Cycloaddition Behavior of Spirocyclic Carbonyl Ylides. Application to the Synthesis of the Pterosin Family of Sesquiterpenes

  摘要：

  The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)cyclopropane and ethyl 3-(1-acetyl-cyclopropyl)-2-diazo-3-oxopropiolate with various dipolarophiles afforded dipolar cycloadducts in good yield. The reaction involves the formation of a rhodium carbenoid and subsequent transannular cyclization of the electrophilic carbon onto the adjacent keto group to generate a five-membered cyclic carbonyl ylide which undergoes a subsequent dipolar cycloaddition reaction. The regiochemical results encountered can be rationalized on the basis of FMO considerations. For carbonyl ylides, the HOMO dipole is dominant for reactions with electron deficient dipolarophiles, while the LUMO becomes important for cycloaddition to more electron rich species. A short synthesis of several members of the pterosin family of sesquiterpenes is described in which the key step involves a dipolar cycloaddition using a carbonyl ylide. The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)-cyclopropane with cyclopentenone afforded a dipolar cycloadduct in good yield as a 4:1 mixture of diastereomers. Treatment of the major cycloadduct with triphenylphosphonium bromide in the presence of sodium hydride gave the expected Wittig product. The reaction of this compound with acid in the presence of various solvents gave rise to several members of the pterosin family. The overall sequence of reactions can best be described as proceeding by an initial oxy-bridge ring opening followed by dehydration and a subsequent acid-catalyzed cyclopropyl ring opening. The facility of the process is undoubtedly related to the aromaticity gained in the final step.

  DOI：

  10.1021/jo951371e
• 作为产物：
  描述：

  1,4-二碘代丁烷 、 乙酰乙酸甲酯 在 potassium carbonate 作用下， 以 二甲基亚砜 为溶剂， 以99%的产率得到甲基1-乙酰基环戊烷羧酸酯
  参考文献：
  名称：

  Generation and Cycloaddition Behavior of Spirocyclic Carbonyl Ylides. Application to the Synthesis of the Pterosin Family of Sesquiterpenes

  摘要：

  The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)cyclopropane and ethyl 3-(1-acetyl-cyclopropyl)-2-diazo-3-oxopropiolate with various dipolarophiles afforded dipolar cycloadducts in good yield. The reaction involves the formation of a rhodium carbenoid and subsequent transannular cyclization of the electrophilic carbon onto the adjacent keto group to generate a five-membered cyclic carbonyl ylide which undergoes a subsequent dipolar cycloaddition reaction. The regiochemical results encountered can be rationalized on the basis of FMO considerations. For carbonyl ylides, the HOMO dipole is dominant for reactions with electron deficient dipolarophiles, while the LUMO becomes important for cycloaddition to more electron rich species. A short synthesis of several members of the pterosin family of sesquiterpenes is described in which the key step involves a dipolar cycloaddition using a carbonyl ylide. The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)-cyclopropane with cyclopentenone afforded a dipolar cycloadduct in good yield as a 4:1 mixture of diastereomers. Treatment of the major cycloadduct with triphenylphosphonium bromide in the presence of sodium hydride gave the expected Wittig product. The reaction of this compound with acid in the presence of various solvents gave rise to several members of the pterosin family. The overall sequence of reactions can best be described as proceeding by an initial oxy-bridge ring opening followed by dehydration and a subsequent acid-catalyzed cyclopropyl ring opening. The facility of the process is undoubtedly related to the aromaticity gained in the final step.

  DOI：

  10.1021/jo951371e

文献信息

• N-Heterocyclic olefins as efficient phase-transfer catalysts for base-promoted alkylation reactions
  作者：Marcus Blümel、Reece D. Crocker、Jason B. Harper、Dieter Enders、Thanh V. Nguyen

  DOI：10.1039/c6cc03771b

  日期：——

  N-Heterocyclic Olefins (NHOs) have very recently emerged as efficient promoters for several chemical reactions due to their strong Bronsted/Lewis basicities. Here we report the novel application of NHOs as efficient...

  N-杂环烯烃（NHOs）由于其强大的Bronsted / Lewis基础性，最近已成为多种化学反应的有效促进剂。在这里，我们将NHO的新颖应用报告为高效...
• Synthesis of Substituted Indolines through Photocatalyzed Decarboxylative Radical Arylation
  作者：Jean-Philippe Fontaine、Vincent Lapointe、Marion Filliâtre、Guillaume Bélanger

  DOI：10.1021/acs.joc.2c02627

  日期：——

  alkyl radical generation and cyclization to prepare substituted indolines in a green, metal-free procedure. This method complements the Fischer indolization, metal-catalyzed couplings, and photocatalyzed radical addition and cyclization. A wide range of functional groups is tolerated, including aryl halides, that would not be compatible with most existing methods. Electronic bias and substitution were

  我们报告了一种新的光催化远程烷基自由基生成和环化，以绿色、无金属的程序制备取代的二氢吲哚。该方法补充了 Fischer 吲哚化、金属催化偶联和光催化自由基加成和环化。可以容忍各种官能团，包括芳基卤化物，这与大多数现有方法不兼容。研究了电子偏差和替代以证明二氢吲哚形成中的完全区域控制和高度化学控制。
• Generation and Cycloaddition Behavior of Spirocyclic Carbonyl Ylides. Application to the Synthesis of the Pterosin Family of Sesquiterpenes
  作者：Albert Padwa、Erin A. Curtis、Vincent P. Sandanayaka

  DOI：10.1021/jo951371e

  日期：1996.1.1

  The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)cyclopropane and ethyl 3-(1-acetyl-cyclopropyl)-2-diazo-3-oxopropiolate with various dipolarophiles afforded dipolar cycloadducts in good yield. The reaction involves the formation of a rhodium carbenoid and subsequent transannular cyclization of the electrophilic carbon onto the adjacent keto group to generate a five-membered cyclic carbonyl ylide which undergoes a subsequent dipolar cycloaddition reaction. The regiochemical results encountered can be rationalized on the basis of FMO considerations. For carbonyl ylides, the HOMO dipole is dominant for reactions with electron deficient dipolarophiles, while the LUMO becomes important for cycloaddition to more electron rich species. A short synthesis of several members of the pterosin family of sesquiterpenes is described in which the key step involves a dipolar cycloaddition using a carbonyl ylide. The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)-cyclopropane with cyclopentenone afforded a dipolar cycloadduct in good yield as a 4:1 mixture of diastereomers. Treatment of the major cycloadduct with triphenylphosphonium bromide in the presence of sodium hydride gave the expected Wittig product. The reaction of this compound with acid in the presence of various solvents gave rise to several members of the pterosin family. The overall sequence of reactions can best be described as proceeding by an initial oxy-bridge ring opening followed by dehydration and a subsequent acid-catalyzed cyclopropyl ring opening. The facility of the process is undoubtedly related to the aromaticity gained in the final step.