ethyl 2-methylcyclohepta-2,4,6-triene-1-carboxylate | 75862-78-1

• 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-methylcyclohepta-2,4,6-triene-1-carboxylate
• 英文别名: ethyl 2-methyl-2,4,6-cycloheptatrienecarboxylate
• CAS: 75862-78-1
• 化学式: C₁₁H₁₄O₂
• 分子量: 178.231
• InChiKey: OMZCDWGEJAFJIK-UHFFFAOYSA-N

物化性质

• 沸点：
  248.0±29.0 °C(Predicted)
• 密度：
  1.011±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  重氮乙酸乙酯 、 甲苯 在 辛酸铑 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.33h， 生成 ethyl 2-methylcyclohepta-2,4,6-triene-1-carboxylate 、 ethyl 3-methylcyclohepta-1,3,5-triene-7-carboxylate
  参考文献：
  名称：

  区域选择性和对映选择性分子间布氏环的扩展

  摘要：

  使用连续流动报道了区域选择性和对映选择性分子间布氏环膨胀的第一个例子。在流动条件下，反应的实用性和范围得到了极大的改善。重氮乙酸乙酯与对称和不对称芳烃的反应以良好的收率和优异的区域选择性提供了环庚烯。不对称分子间布氏反应的第一个例子已证明对二取代重氮酯具有良好的至优异的对映选择性。不对称反应以绝对的区域选择性进行，得到具有全碳季中心的环庚烯。

  DOI：

  10.1021/acs.orglett.7b02537

文献信息

• 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。
• Mechanistic Studies on Gold-Catalyzed Direct Arene C–H Bond Functionalization by Carbene Insertion: The Coinage-Metal Effect
  作者：Manuel R. Fructos、Maria Besora、Ataualpa A. C Braga、M. Mar Díaz-Requejo、Feliu Maseras、Pedro J. Pérez

  DOI：10.1021/acs.organomet.6b00604

  日期：2017.1.9

  The catalytic functionalization of the C-sp(2)-H bond of benzene by means of the insertion of the CHCO2Et group from ethyl diazoacetate (N-2=CHCO2Et) has been studied with the series of coinage-metal complexes IPrMCl (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene) and NaBAr4F (BAr4F = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). For Cu and Ag, these examples constitute the first use of such metals toward this transformation, which also provides ethyl cyclohepta-2,4,6-trienecarboxylate as a byproduct from the so-called Buchner reaction. In the case of methyl-substituted benzenes, the reaction exclusively proceeds onto the aromatic ring, the C-sp(2)-H bond remaining unreacted. A significant coinage-metal effect has been observed, since the gold catalyst favors the formation of the insertion product into the C-sp(2)-H bond whereas copper and silver preferentially induce the formation of the cycloheptatriene derivative. Experimental studies and theoretical calculations have explained the observed selectivity in terms of the formation of a common Wheland intermediate, resembling an electrophilic aromatic substitution, from which the reaction pathway evolves into two separate routes to each product.
• Transition-metal-catalyzed reactions of diazo compounds. 2. Addition to aromatic molecules: catalysis of Buchner's synthesis of cycloheptatrienes
  作者：A. J. Anciaux、A. Demonceau、A. F. Noels、A. J. Hubert、R. Warin、P. Teyssie

  DOI：10.1021/jo00318a010

  日期：1981.2
• 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.