7,8-dicarbomethoxybicyclo<4.2.1>nona-2,4,7-triene

• 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: 7,8-dicarbomethoxybicyclo<4.2.1>nona-2,4,7-triene
• 英文别名: dimethyl bicyclo[4.2.1]nona-2,4,7-trien-7,8-dicarboxylate；Dimethyl bicyclo[4.2.1]nona-2,4,7-triene-7,8-dicarboxylate
• 化学式: C₁₃H₁₄O₄
• 分子量: 234.252
• InChiKey: CLJUAUFZZKEGES-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  环庚三烯 、 丁炔二酸二甲酯 在 三异丙基亚磷酸酯 、 cobalt(II) bromide 、 zinc(II) iodide 、 锌 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以21%的产率得到7,8-dicarbomethoxybicyclo<4.2.1>nona-2,4,7-triene
  参考文献：
  名称：

  钴催化内部炔烃和末端烯烃与环庚三烯的[6 + 2]环加成反应

  摘要：

  描述了钴与内部炔烃以及末端烯烃的环庚三烯的[6 + 2]环加成反应。环加成过程最有效地是由二氯甲烷中的二溴化钴[双（亚磷酸三异丙酯）]络合物作为选择的溶剂来催化的。在钴催化的环庚三烯与降冰片烯的反应中，分离出出乎意料的三环[2 + 2]环加成产物，收率很高。 炔烃-烯烃-钴-环加成反应-二烯

  DOI：

  10.1055/s-0029-1216900

文献信息

• Metal-Mediated [6 + 2] Cycloadditions of Alkynes to Cycloheptatriene and N-Carbethoxyazepine
  作者：Karen Chaffee、Pei Huo、John B. Sheridan、Anthony Barbieri、Arnis Aistars、Roger A. Lalancette、Robert L. Ostrander、Arnold L. Rheingold

  DOI：10.1021/ja00112a005

  日期：1995.2

  UV photolysis of [(eta(6)-C(7)H(7)R)Cr(Co)(3)] (1, R = H, Ph, CH(CO(2)Me)(2)) and R'C = CR' (R' = Ph, Tol, SiMe(3), Et) in toluene or n-hexane gives the [6 + 2] cycloadducts [(eta(2:4)-C9H7(R)R'(2))Cr(CO)(3)] (2). Heating 2 in toluene releases the 7,8-disubstituted bicyclo[4.2.1]nona-2,4,7-trienes 3 and [(eta(6)-C(6)H(5)Me)Cr(CO)(3)]. Irradiation of solutions of 1 and dimethyl acetylenedicarboxylate at 0 degrees C yields the bicyclotriene as the major product but no organometallic complex. The diphenyl derivative 2a undergoes a reversible intramolecular metal migration to the eta(6)-aryl species 4. Irradiation of the azepine complex [(eta(6)-C6H6N(CO(2)Et))Cr(CO)(3)] (5) and R'C = CR' (R' = Ph, SiMe(3)) in toluene also forms [6 + 2] cycloadducts [(eta(2:4)-C8H6N(CO2Er)R'(2))Cr(CO)(3)] (6). The heterobicyclotrienes 7 are isolated from 6 by treatment with iodine (R' = SiMe(3)) or by hearing in toluene (R' = Ph). X-ray crystal structures are reported for 6b (R' = SiMe(3)) [orthorhombic, P2(1)2(1)2(1), a = 8.871(1), b = 10.148(1), and c = 26.017(4) Angstrom, R = 0.041 for 2500 independent reflections] and a byproduct (8) that results from the endo [6 + 4] cycloaddition of N-carbethoxyazepine to 5; monoclinic, P2(1)/c, a = 10.665(9), b = 14.976(7), and c = 13.004(7) Angstrom, beta = 100.05(7)degrees, R = 0.047 for 1044 independent reflections. Heating cycloheptatriene and alkynes R'C = CR' (R' = SiMe(3), Me, Et) in dibutyl ether with a catalytic amount of Cr(CO)(6) or Fe-2(CO)(9) also gives good yields of the [6 + 2] cycloadducts 3, whereas the thermal reaction with dimethyl acetylenedicarboxylate in the presence of Cr(CO)(6) gives the known norcaradiene [4 + 2] adduct 9.
• Cobalt-Catalysed [6+2] Cycloaddition of Internal Alkynes and Terminal ­Alkenes with Cycloheptatriene
  作者：Gerhard Hilt、Anna Paul、Christoph Hengst

  DOI：10.1055/s-0029-1216900

  日期：2009.10

  cobalt-catalysed [6+2] cycloaddition of cycloheptatriene with internal alkynes as well as with terminal alkenes is described. The cycloaddition process is most efficiently catalysed by cobalt dibromide[bis(triisopropylphosphite)] complexes in dichloromethane as the solvent of choice. In the cobalt-catalysed reaction of cycloheptatriene with norbornene an unexpected tricyclic [2+2] cycloaddition product was

  描述了钴与内部炔烃以及末端烯烃的环庚三烯的[6 + 2]环加成反应。环加成过程最有效地是由二氯甲烷中的二溴化钴[双（亚磷酸三异丙酯）]络合物作为选择的溶剂来催化的。在钴催化的环庚三烯与降冰片烯的反应中，分离出出乎意料的三环[2 + 2]环加成产物，收率很高。 炔烃-烯烃-钴-环加成反应-二烯