dimethyl (E)-2-(4-methoxybenzylidene)cyclopropane-1,1-dicarboxylate | 1089186-29-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: dimethyl (E)-2-(4-methoxybenzylidene)cyclopropane-1,1-dicarboxylate
• CAS: 1089186-29-7
• 化学式: C₁₅H₁₆O₅
• 分子量: 276.289
• InChiKey: IYMRAXUYMJMBEC-DHZHZOJOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.81
• 重原子数：
  20.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  dimethyl (E)-2-(4-methoxybenzylidene)cyclopropane-1,1-dicarboxylate 、 异丙烯基溴化镁 以 四氢呋喃 为溶剂， 反应 1.0h， 以79%的产率得到methyl (E)-1-methacryloyl-2-(4-methoxybenzylidene)cyclopropane-1-carboxylate
  参考文献：
  名称：

  Catalytic, Formal Homo-Nazarov-Type Cyclizations of Alkylidene Cyclopropane-1,1-Ketoesters: Access to Functionalized Arenes and Heteroaromatics

  摘要：

  A catalytic, formal homo-Nazarov-type cyclization of alkylidene cyclopropanes (ACPs) to give functionalized arenes and heteroaromatics is reported. In the presence of a Lewis acid catalyst, the ACP 1,1-ketoesters undergo distal bond cleavage to afford an allyl cation intermediate. Adjacent m-attack on the ally! cation then provides a six-membered ring that undergoes rapid aromatization. In these cases, benzenoid products are formed in up to 98% yield. Strategic choice of the substitution about the ACP allows for the generation of other useful isomeric products in good yields.

  DOI：

  10.1021/ol501676q
• 作为产物：
  描述：

  2-叠氮丙二酸二甲酯 、 4-methoxylphenylallene 在 bis{rhodium[3,3'-(1,3-phenylene)bis(2,2-dimethylpropanoic acid)]} 作用下， 以 二氯甲烷 为溶剂， 以77%的产率得到dimethyl (E)-2-(4-methoxybenzylidene)cyclopropane-1,1-dicarboxylate
  参考文献：
  名称：

  Catalytic, Formal Homo-Nazarov-Type Cyclizations of Alkylidene Cyclopropane-1,1-Ketoesters: Access to Functionalized Arenes and Heteroaromatics

  摘要：

  A catalytic, formal homo-Nazarov-type cyclization of alkylidene cyclopropanes (ACPs) to give functionalized arenes and heteroaromatics is reported. In the presence of a Lewis acid catalyst, the ACP 1,1-ketoesters undergo distal bond cleavage to afford an allyl cation intermediate. Adjacent m-attack on the ally! cation then provides a six-membered ring that undergoes rapid aromatization. In these cases, benzenoid products are formed in up to 98% yield. Strategic choice of the substitution about the ACP allows for the generation of other useful isomeric products in good yields.

  DOI：

  10.1021/ol501676q

文献信息

• Lewis acid-catalyzed nucleophilic ring-opening/intramolecular Conia-ene reactions of methylenecyclopropane 1,1-diesters with propargyl alcohols
  作者：Bao Hu、Jun Ren、Zhongwen Wang

  DOI：10.1016/j.tet.2010.11.048

  日期：2011.1

  Lewis acid-catalyzed nucleophilic ring opening of methylenecyclopropane (MCP) 1,1-diesters with propargyl alcohols. Unlike the proximal-bond cleavage mode observed in cases of unactivated MCPs, the intrinsic characteristic of MCP 1,1-diesters gave a regiospecific distal-bond cleavage under attack of propargyl alcohols as nucleophiles. By combining a subsequent intramolecular Conia-ene reaction, 3,5

  我们提出了路易斯酸催化的炔丙基醇与亚甲基环丙烷（MCP）1,1-二酯的亲核开环。与未激活的MCP情况下观察到的近端键裂解模式不同，MCP 1,1-二酯的内在特征在炔丙醇作为亲核试剂的攻击下产生了区域特异性的远端键裂解。通过结合随后的分子内Conia-ene反应，可以逐步或一锅法获得3,5-二亚甲基四氢吡喃。