ethyl 2,4,6-trimethylcyclohepta-2,4,6-triene-1-carboxylate | 651046-46-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl 2,4,6-trimethylcyclohepta-2,4,6-triene-1-carboxylate
• 英文别名: 2,4,6-Cycloheptatriene-1-carboxylic acid, 2,4,6-trimethyl-, ethyl ester
• CAS: 651046-46-7
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: FBKRTAWEKDAJGH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 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 2,4,6-trimethylcyclohepta-2,4,6-triene-1-carboxylate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 16.0h， 以86%的产率得到(2,4,6-trimethylcyclohepta-2,4,6-trien-1-yl)methanol
  参考文献：
  名称：

  通过铑（II）和金（I）非受体碳烯的（4 + 3）环加成组装复杂的1,4-环庚二烯

  摘要：

  1,3-二烯与Rh（II）和Au（I）非受体乙烯基碳烯的正式（4 + 3）环加成反应分别由乙烯基环庚烯或烷氧炔生成，导致1,4-环庚二烯具有复杂而多样的取代作用包括天然dyctiopterene C'和carota-1,4-diene的羟基化衍生物。呈现了完整的机理图，其中显示了Au（I）和Rh（II）非受体乙烯基碳烯经历了乙烯基环丙烷化/ Cope重排或以未经证实的方式发生的直接（4 + 3）环加成反应。

  DOI：

  10.1002/anie.202012092
• 作为产物：
  描述：

  重氮乙酸乙酯 、 均三甲苯 在 dirhodium tetraacetate 作用下， 以 二氯甲烷 为溶剂， 反应 60.0h， 以77%的产率得到ethyl 2,4,6-trimethylcyclohepta-2,4,6-triene-1-carboxylate
  参考文献：
  名称：

  Retro-Buchner反应供体铑卡宾

  摘要：

  卡宾铑是一系列环加成反应和插入反应的关键中间体。在此，我们报告了通过7-取代的1,3,5-环庚庚烯的脱碳而生成的第一代供体Rh II卡宾。这一发现开启了改良的布氏环丙烷化反应的逆序，用于广谱合成烯丙基硅烷的Si-H插入反应以及醛类乙烯基化的新方法。最后一种策略导致了E-多烯的迭代合成的发展，以及navenones B和C的总合成。

  DOI：

  10.1002/anie.201813512

文献信息

• Cyclopropanation by Gold- or Zinc-Catalyzed Retro-Buchner Reaction at Room Temperature
  作者：Mauro Mato、Bart Herlé、Antonio M. Echavarren

  DOI：10.1021/acs.orglett.8b01791

  日期：2018.7.20

  gold(I)-catalyzed retro-Buchner–cyclopropanation sequence and the first zinc(II)-catalyzed version of this process, which uses inexpensive ZnBr2 as catalyst, have been developed. This led to a broad-scope cyclopropanation of both activated and unactivated alkenes, including late-stage derivatization of biologically relevant compounds, and to the total synthesis of (±)-lactobacillic acid.

  通过设计第二代更具反应性的7-取代的1,3,5-环庚烯，室温金（I）催化的逆布赫纳环丙烷化序列和该工艺的第一个锌（II）催化形式已经开发出使用廉价的ZnBr 2作为催化剂的催化剂。这导致了活化和未活化烯烃的广谱环丙烷化，包括生物相关化合物的后期衍生化，以及（±）-乳酸杆菌酸的总合成。
• Synthesis of new copper(<scp>i</scp>) complexes with tris(2-pyridyl) ligands. Applications to carbene and nitrene transfer reactions
  作者：Julio Pérez、Dolores Morales、Luis A. García-Escudero、Héctor Martínez-García、Daniel Miguel、Pablo Bernad

  DOI：10.1039/b812604f

  日期：——

  New copper(I) complexes with tris(2-pyridyl)methane (TPC), tris(2-pyridyl)methoxymethane (TPM) and tris(2-pyridyl)amine (TPN) ligands have been synthesized and characterized, including structural determinations by X-ray diffraction of some examples. Their activity as catalysts in carbene and nitrene transfer reactions was studied.

  合成并表征了具有三（2-吡啶基）甲烷（TPC），三（2-吡啶基）甲氧基甲烷（TPM）和三（2-吡啶基）胺（TPN）配体的新型铜（I）配合物，包括通过X射线衍射的一些例子。研究了它们在卡宾和氮烯转移反应中作为催化剂的活性。
• Kinetic Separation and Asymmetric Reactions of Norcaradiene Cycloadducts: Facilitated Access via H₂O-Accelerated Cycloaddition
  作者：William D. Mackay、Jeffrey S. Johnson

  DOI：10.1021/acs.orglett.5b03577

  日期：2016.2.5

  We exploit the Buchner reaction to access 1,2-disubstituted cyclohexadiene synthons (norcaradienes), which participate in H2O-accelerated cycloaddition with dieneophiles to provide cyclopropyl-fused [2.2.2]-bicyclooctene derivatives in good yields. Regioisomeric mixtures can be kinetically separated by exploiting different reaction rates in Diels Alder reactions. Meso-Diels-Alder products may be enantioselectively desymmetrized, providing highly substituted cyclohexanes with up to seven contiguous stereocenters.
• Büchner Reactions Catalyzed by a Silver(I) Pyridylpyrrolide: Understanding Arene C═C Insertion Selectivity
  作者：Nobuyuki Komine、Jaime A. Flores、Kuntal Pal、Kenneth G. Caulton、Daniel J. Mindiola

  DOI：10.1021/om301240d

  日期：2013.6.10

  The complex Ag-3(mu(2)-3,5-(CF3)(2)PyrPy)(3) (3,5-(CF3)(2)PyrPy = 2,2'-pyridylpyrrolide(1-) ligand) catalytically promotes the insertion of the carbene of ethyl diazoacetate (EDA), at room temperature, into the C=C bond of a series of arenes to ultimately ring-open them and form the corresponding cycloheptatrienes. In one case, the norcaradiene intermediate can be isolated, while regioselective C=C insertion can be promoted with certain arene substrates. The mechanism of C=C insertion, preference over C-H insertion, and origin of C=C regioselectivity has been probed by a combination of experimental and theoretical studies.
• A silver-catalyzed Büchner reaction
  作者：Carl J. Lovely、R. Greg Browning、Vivek Badarinarayana、H.V. Rasika Dias

  DOI：10.1016/j.tetlet.2005.02.052

  日期：2005.4

  A silver scorpionate complex, derived from the highly fluorinated [HB(3,5-(CF3)(2)PZ)3](-), catalyzes the addition of ethyl diazoacetate to benzene rings, providing norcaradienes, which undergo elect rocyclization to provide the corresponding cycloheptatriene. These reactions are surprisingly selective for addition to the aromatic moiety rather than C-H insertion. (c) 2005 Elsevier Ltd. All rights reserved.