4,7-dimethylindane-2,2-dicarboxylic acid dimethyl ester

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: 4,7-dimethylindane-2,2-dicarboxylic acid dimethyl ester
• 英文别名: 4,7-dimethylindan-2,2-dicarboxylic acid dimethyl ester；Dimethyl 4,7-dimethyl-1,3-dihydroindene-2,2-dicarboxylate
• 化学式: C₁₅H₁₈O₄
• 分子量: 262.306
• InChiKey: KSIKQCUSAMJOLD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 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：

  乙烯基正丁醚 、 dimethyl 2,2-di(but-2-yn-1-yl)malonate 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 氢气 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 二氯甲烷 为溶剂， 以93%的产率得到4,7-dimethylindane-2,2-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  在阳离子Rh（I）/ BINAP催化的化学和区域选择性形式的正式跨炔烃环三聚反应中，作为气态炔烃当量的市售液体烯醇醚和乙酸酯

  摘要：

  阳离子铑（I）/ BINAP络合物可催化1,6-和1,7-二炔与烯醇醚或乙烯酮缩醛的部分分子内[2 + 2 + 2]环加成反应，从而以高收率得到取代的苯。相同的催化剂还催化两种不同的单炔与烯醇乙酸酯的完全分子间[2 + 2 + 2]环加成反应，从而以良好的收率和完全的区域选择性得到三和四取代的苯。在当前的铑催化的正式跨炔烃环三聚反应中，可商购的液体烯醇醚和乙酸酯可用作气态炔烃的通用等同物。

  DOI：

  10.1016/j.tet.2009.02.047

文献信息

• Liquid Enol Ethers and Acetates as Gaseous Alkyne Equivalents in Rh-Catalyzed Chemo- and Regioselective Formal Cross-Alkyne Cyclotrimerization
  作者：Hiromi Hara、Masao Hirano、Ken Tanaka

  DOI：10.1021/ol800813g

  日期：2008.6.1

  A cationic rhodium(I)/rac-BINAP complex catalyzes chemo- and regioselective formal cross-cyclotrimerizations of alkynes with enol ethers or acetates. Commercially available and cheap liquid enol ethers and acetates could be used as convenient gaseous alkyne equivalents in the present rhodium catalyses.

  阳离子铑（I）/ rac-BINAP络合物催化炔烃与烯醇醚或乙酸酯的化学和区域选择性形式的交叉环三聚反应。市售和廉价的液态烯醇醚和乙酸酯可用作本发明铑催化剂中的方便的气态炔烃当量。
• Iridium Complex-Catalyzed [2+2+2] Cycloaddition of α,ω-Diynes with Monoynes and Monoenes
  作者：Satoko Kezuka、Shigeru Tanaka、Toshihito Ohe、Yoshihiko Nakaya、Ryo Takeuchi

  DOI：10.1021/jo051874c

  日期：2006.1.1

  [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.
• Commercially available liquid enol ethers and acetates as gaseous alkyne equivalents in cationic Rh(I)/BINAP-catalyzed chemo- and regioselective formal cross-alkyne cyclotrimerizations
  作者：Hiromi Hara、Masao Hirano、Ken Tanaka

  DOI：10.1016/j.tet.2009.02.047

  日期：2009.6

  A cationic rhodium(I)/BINAP complex catalyzes partial intramolecular [2+2+2] cycloadditions of 1,6- and 1,7-diynes with enol ethers or a ketene acetal giving substituted benzenes in good yields. The same catalyst also catalyzes complete intermolecular [2+2+2] cycloadditions of two different monoynes with enol acetates giving tri- and tetrasubstituted benzenes in good yields with complete regioselectivity

  阳离子铑（I）/ BINAP络合物可催化1,6-和1,7-二炔与烯醇醚或乙烯酮缩醛的部分分子内[2 + 2 + 2]环加成反应，从而以高收率得到取代的苯。相同的催化剂还催化两种不同的单炔与烯醇乙酸酯的完全分子间[2 + 2 + 2]环加成反应，从而以良好的收率和完全的区域选择性得到三和四取代的苯。在当前的铑催化的正式跨炔烃环三聚反应中，可商购的液体烯醇醚和乙酸酯可用作气态炔烃的通用等同物。