2-ethyl 1-methyl 4-(diphenylmethylene)-1-phenylcyclopent-2-ene-1,2-dicarboxylate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-ethyl 1-methyl 4-(diphenylmethylene)-1-phenylcyclopent-2-ene-1,2-dicarboxylate
• 英文别名: 2-O-ethyl 1-O-methyl 4-benzhydrylidene-1-phenylcyclopent-2-ene-1,2-dicarboxylate
• 化学式: C₂₉H₂₆O₄
• 分子量: 438.523
• InChiKey: RGSCHLADHMKAGV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  地芬尼多杂质9 在 三丁基膦 、 溴 、 溶剂黄146 、 三乙胺 作用下， 以 四氢呋喃 、 氯仿 、 甲苯 、 乙腈 、 苯 为溶剂， 反应 14.08h， 生成 2-ethyl 1-methyl 4-(diphenylmethylene)-1-phenylcyclopent-2-ene-1,2-dicarboxylate
  参考文献：
  名称：

  5,5-二芳基戊基2,3,4-三烯酸乙酯与芳族醛和α，β-不饱和羰基化合物的膦催化区域选择性[3 + 2]环加成反应

  摘要：

  AbstractTributylphosphine‐catalyzed regioselective [3+2] cycloadditions between ethyl 5,5‐diarylpenta‐2,3,4‐trienoate 1 and various aromatic aldehydes 2 to produce a wide variety of polysubstituted 2,5‐dihydrofurans 3, and between 1 and β‐unsubstituted α,β‐unsaturated carbonyl compounds 5 to give polysubstituted cyclopentenes 6 with a quaternary carbon center, are reported. In both cases the reaction partners approach each other via the sterically less hindered orientation to afford the target products in excellent regioselectivity. The reaction mechanism involved first the generation of a zwitterionic intermediate between the butatriene 1 and PBu3. For the formation of 2,5‐dihydrofurans 3, the preferred cyclization mode encompassed the nucleophilic attack of the α‐position of butatriene to the aldehydic carbon of 2, followed by the ring closure between the aldehydic oxygen of 2 and the γ‐position of butatriene, which is the first report of a normal [3+2] cycloaddition between cumulenes and aldehydes. For the formation of cyclopentenes 6, the reaction involved attack of the γ‐position of the butatriene to the electron‐deficient β‐position of the α,β‐unsaturated carbonyl compounds 5, followed by the ring closure between the α‐position of 5 and the α‐position of butatriene, which shows a different regioselectivity to the previously reported [3+2] cycloadditions between butatriene and olefins.magnified image

  DOI：

  10.1002/adsc.201301000

文献信息

• A Phosphine-Catalyzed Regioselective [3+2] Cycloaddition of Ethyl 5,5-Diarylpenta-2,3,4-trienoate with Aromatic Aldehydes and α,β-Unsaturated Carbonyl Compounds
  作者：Lu-Feng Wang、Xiao-Ping Cao、Zi-Fa Shi、Peng An、Hak-Fun Chow

  DOI：10.1002/adsc.201301000

  日期：2014.11.3

  AbstractTributylphosphine‐catalyzed regioselective [3+2] cycloadditions between ethyl 5,5‐diarylpenta‐2,3,4‐trienoate 1 and various aromatic aldehydes 2 to produce a wide variety of polysubstituted 2,5‐dihydrofurans 3, and between 1 and β‐unsubstituted α,β‐unsaturated carbonyl compounds 5 to give polysubstituted cyclopentenes 6 with a quaternary carbon center, are reported. In both cases the reaction partners approach each other via the sterically less hindered orientation to afford the target products in excellent regioselectivity. The reaction mechanism involved first the generation of a zwitterionic intermediate between the butatriene 1 and PBu3. For the formation of 2,5‐dihydrofurans 3, the preferred cyclization mode encompassed the nucleophilic attack of the α‐position of butatriene to the aldehydic carbon of 2, followed by the ring closure between the aldehydic oxygen of 2 and the γ‐position of butatriene, which is the first report of a normal [3+2] cycloaddition between cumulenes and aldehydes. For the formation of cyclopentenes 6, the reaction involved attack of the γ‐position of the butatriene to the electron‐deficient β‐position of the α,β‐unsaturated carbonyl compounds 5, followed by the ring closure between the α‐position of 5 and the α‐position of butatriene, which shows a different regioselectivity to the previously reported [3+2] cycloadditions between butatriene and olefins.magnified image