ethyl trans-2,3-bis(4-methylphenyl)cyclopropanecarboxylate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: ethyl trans-2,3-bis(4-methylphenyl)cyclopropanecarboxylate
• 英文别名: ethyl 2,3-di(p-tolyl)cyclopropanecarboxylate；ethyl 2,3-di-p-tolylcyclopropane-1-carboxylate；ethyl (2S,3S)-2,3-bis(4-methylphenyl)cyclopropane-1-carboxylate
• 化学式: C₂₀H₂₂O₂
• 分子量: 294.393
• InChiKey: SUCPRJDDYXCMFE-ROUUACIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl trans-2,3-bis(4-methylphenyl)cyclopropanecarboxylate 在 sodium hydroxide 、 叠氮磷酸二苯酯 、 乙酸酐 、 溶剂黄146 、 三乙胺 、 sodium nitrite 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 10.55h， 生成 1,3-di-p-tolylpropa-1,2-diene
  参考文献：
  名称：

  Electron demand in the transition state of the cyclopropylidene to allene ring opening

  摘要：

  The electronic structure of the transition state for the cyclopropylidene to allene conversion has been probed. The methodology involved the relative rates of ring opening vs trapping by MeOH for a series of variously substituted 2,3-diarylcyclopropylidenes. With the assumption that the rate of trapping was unaffected by substituents, a Hammett correlation was constructed. The negative value (-0.72) for rho indicated that the carbenic center attracts electron density in the ring-opening transition state, much like the cyclopropyl cation to allyl cation transition state. Temperature-dependent studies showed that the observed preference for ring opening was driven by entropy factors. Also, using reasonable estimates for the close to diffusion-controlled trapping activation enthalpies, the derived enthalpies for ring opening were in close agreement with the best theoretical values.

  DOI：

  10.1021/jo00049a042
• 作为产物：
  描述：

  重氮乙酸乙酯 、 4,4'-dimethylstilbene 在 tris(1,10-phenanthroline)iron(III) tris(hexafluorophosphate) 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 3.0h， 以87%的产率得到ethyl trans-2,3-bis(4-methylphenyl)cyclopropanecarboxylate
  参考文献：
  名称：

  铁（III）-菲咯啉配合物对烯烃自由基阳离子的环加成反应

  摘要：

  使用铁（III）-菲咯啉配合物对富电子烯烃进行单电子氧化可产生亲电子烯烃自由基阳离子，从而促进了重氮化合物与自由基阳离子[2 + 1]的高效环加成反应。随后的链增长得到三和四取代的环丙烷。该方法还扩展到了与乙烯基重氮酯的[3 + 2]环加成反应，验证了这种可持续的第一行过渡金属铁系统的单电子氧化还原反应。

  DOI：

  10.1002/adsc.202000191

文献信息

• Radical Cation Cyclopropanations via Chromium Photooxidative Catalysis
  作者：Francisco J. Sarabia、Eric M. Ferreira

  DOI：10.1021/acs.orglett.7b01095

  日期：2017.6.2

  The chromium photocatalyzed cyclopropanation of diazo reagents with electron-rich alkenes is described. The transformation occurs under mild conditions and features specific distinctions from traditional diazo-based cyclopropanations (e.g., avoiding β-hydride elimination, chemoselectivity considerations, etc.). The reaction appears to work most effectively using chromium catalysis, and a number of

  描述了重氮试剂与富电子烯烃的铬光催化环丙烷化反应。该转化发生在温和的条件下，并具有与传统重氮基环丙烷化的特定区别（例如，避免β-氢化物消除、化学选择性考虑等）。该反应似乎在铬催化下最有效地进行，并且可以以通常良好的产率获得许多修饰的环丙烷。
• 철 촉매를 이용한 라디칼 양이온 고리화 첨가반응을 통하여 사이클로프로판 또는 사이클로펜텐 유도체를 합성하는 방법
  申请人：University-Industry Cooperation Group of Kyung Hee University 경희대학교 산학협력단(220040073623) BRN ▼135-82-10789

  公开号：KR20210127306A

  公开（公告）日：2021-10-22

  본 개시 내용에서는 Fe(III) 착체를 일전자 산화제로 이용하여, 전자-풍부한 알켄 화합물을 산화시켜 라디칼 양이온 중간체를 형성한 다음, 디아조 화합물과의 고리화 첨가 반응을 유도함으로써 3각 고리(사이클로프로판) 또는 5각 고리(사이클로펜텐) 화합물(또는 유도체)를 합성하는 방법이 기재된다.

  本发明内容涉及利用Fe(III)络合物作为一电子氧化剂，氧化富电子烯化合物形成自由基阳离子中间体，然后通过诱导与重氮化合物的环加成反应来合成三元环（环丙烷）或五元环（环戊二烯）化合物（或衍生物）的方法。
• Mechanistic Criteria for Cation Radical Reactions: Aminium Salt-Catalyzed Cyclopropanation
  作者：Wang Yueh、Nathan L. Bauld

  DOI：10.1021/ja00126a007

  日期：1995.5

  Mechanistic studies of the cyclopropanation of a series of trans-stilbenes by ethyl diazoacetate catalyzed by two different triarylaminium salts decisively confirm a cation radical mechanism and rule out a hypothetical electrophilic mechanism. The elucidation of key aspects of these cation radical mechanisms, including kinetic vs equilibrium control of ionization and chain vs catalytic mechanisms, has also been achieved for these systems. New mechanistic criteria for the positive identification of cation radical mechanisms are proposed.
• Yueh, Wang; Sarker, Haripada; Bauld, Nathan L., Journal of the Chemical Society. Perkin transactions II, 1995, # 9, p. 1715 - 1716
  作者：Yueh, Wang、Sarker, Haripada、Bauld, Nathan L.

  DOI：——

  日期：——
• Cycloaddition Reactions of Alkene Radical Cations using Iron(III)‐Phenanthroline Complex
  作者：Yong Hyun Cho、Jae Hyung Kim、Hyeju An、Kwang‐Hyun Ahn、Eun Joo Kang

  DOI：10.1002/adsc.202000191

  日期：2020.5.26

  oxidation of electron‐rich alkenes using the iron(III)‐phenanthroline complex produced electrophilic alkene radical cations, which promoted efficient radical cation [2+1] cycloaddition reactions with diazo compounds. Subsequent chain propagation afforded tri‐ and tetra‐substituted cyclopropanes. This methodology was also expanded to [3+2] cycloaddition reactions with vinyl diazoesters, validating this sustainable

  使用铁（III）-菲咯啉配合物对富电子烯烃进行单电子氧化可产生亲电子烯烃自由基阳离子，从而促进了重氮化合物与自由基阳离子[2 + 1]的高效环加成反应。随后的链增长得到三和四取代的环丙烷。该方法还扩展到了与乙烯基重氮酯的[3 + 2]环加成反应，验证了这种可持续的第一行过渡金属铁系统的单电子氧化还原反应。