dimethyl 4,8-dimethyl-3a,5,7,8a-tetrahydro-1H-indeno[5,6-c]furan-6,6(3H)-dicarboxylate

• 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: dimethyl 4,8-dimethyl-3a,5,7,8a-tetrahydro-1H-indeno[5,6-c]furan-6,6(3H)-dicarboxylate
• 英文别名: Dimethyl 4,8-dimethyl-1,3,3a,5,7,8a-hexahydrocyclopenta[f][2]benzofuran-6,6-dicarboxylate
• 化学式: C₁₇H₂₂O₅
• 分子量: 306.359
• InChiKey: RAVSUAWJSKVGHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 1,2-双(二苯基膦)乙烷 作用下， 以 四氢呋喃 为溶剂， 生成 dimethyl 4,8-dimethyl-3a,5,7,8a-tetrahydro-1H-indeno[5,6-c]furan-6,6(3H)-dicarboxylate
  参考文献：
  名称：

  Iridium Complex-Catalyzed [2+2+2] Cycloaddition of α,ω-Diynes with Monoynes and Monoenes

  摘要：

  [Ir(cod)Cl](2)/DPPE was found to be a new catalyst for the cycloaddition of alpha,omega-diynes with monoynes to give polysubstituted benzene derivatives in high yields. Internal monoynes as well as terminal monoynes could be used. The reaction tolerates a broad range of functional groups such as alcohol, amine, alkene, ether, halogen, and nitrile. The reaction of 1,6-octadiyne derivatives with 1-alkynes gives ortho products and meta products. The regioselectivity could be controlled by the choice of ligand. The reaction with DPPE was meta selective, with meta selectivity of up to 82%. The reaction with DPPF was ortho selective, with ortho selectivity of up to 88%. We propose a mechanism to account for this regioselective cycloaddition. [Ir(cod)Cl-2]2/DPPE also catalyzed the cycloaddition of alpha-omega-diynes with 2,5-dihydrofuran to give bicyclic cyclohexadiene derivatives. The reaction with 2,3-dihydrofuran and n-butyl vinyl ether gave benzene derivatives instead of cyclohexadiene derivatives. We also propose a mechanism to account for this novel aromatization that includes cleavage of the C-O bond.

  DOI：

  10.1021/jo051874c

文献信息

• Rhodium-Catalyzed [2+2+2] Cyclo­addition-Aromatization of 1,6-Di­ynes with Cyclic Enol Ethers at Room Temperature
  作者：Yukimasa Aida、Shino Tooriyama、Yuki Kimura、Hiromi Hara、Yu Shibata、Ken Tanaka

  DOI：10.1002/ejoc.201501282

  日期：2016.1

  A cationic rhodium(I)/BINAP [2,2′-bis(diphenylphosphino)-1,1′-binaphthyl] complex is capable of catalyzing the [2+2+2] cycloaddition–aromatization of 1,6-diynes with cyclic enol ethers (2,3-dihydrofuran and dihydropyran) at room temperature to produce the corresponding aryl alkanol derivatives in good yields. In this process, a conjugated dihydrofuran showed a significantly higher reactivity than a

  阳离子铑(I)/BINAP [2,2'-双(二苯基膦)-1,1'-联萘]复合物能够催化1,6-二炔的[2+2+2]环加成-芳构化烯醇醚（2,3-二氢呋喃和二氢吡喃）在室温下以良好的产率制备相应的芳基烷醇衍生物。在这个过程中，共轭二氢呋喃比非共轭二氢呋喃表现出明显更高的反应性。