2,5-bis(5-benzyloxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)-3-methylpyrrole | 443755-01-9

• 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: 2,5-bis(5-benzyloxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)-3-methylpyrrole
• 英文别名: dibenzyl 3,12 diethyl-2,7,13-trimethylpyrrane-1,14-dicarboxylate；benzyl 4-ethyl-5-[[5-[(3-ethyl-4-methyl-5-phenylmethoxycarbonyl-1H-pyrrol-2-yl)methyl]-4-methyl-1H-pyrrol-2-yl]methyl]-3-methyl-1H-pyrrole-2-carboxylate
• CAS: 443755-01-9
• 化学式: C₃₇H₄₁N₃O₄
• 分子量: 591.75
• InChiKey: UUJFFIBADAHOMU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.3
• 重原子数：
  44
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  100
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,5-bis(5-benzyloxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)-3-methylpyrrole 在 palladium on activated charcoal 氢气 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 20.0 ℃ 、275.8 kPa 条件下， 反应 19.0h， 生成 8,17-diethyl-7,12,18-trimethyl-21-carbabenzo[b]porphyrin
  参考文献：
  名称：

  Conjugated Macrocycles Related to the Porphyrins. 25. Proton NMR Spectroscopic Evidence for a Preferred [18]Annulene Substructure in Carbaporphyrins from the Magnitude of Selected ⁴J_H,H CHCCH₃ Coupling Constants

  摘要：

  Two new benzocarbaporphyrins with four or five alkyl substituents have been synthesized by the "3 + 1" MacDonald methodology. At lower temperatures, the proton NMR spectrum of the asymmetrically substituted carbaporphyrin 8 gave two NH resonances, while carbaporphyrin 9, which retains a plane of symmetry, gave only one resonance of this kind. As no additional peaks were seen for the remaining protons, these data strongly support the proposal that a single tautomer predominates in solution where the two NH protons flank the interior CH. Carbaporphyrin 8, which has a CH=CMe unit on the pyrrolic ring opposite the indene moiety, gave a long-range coupling constant of (4)J(Me,H) = 1.3-1.4 Hz. On the other hand, the CH=CMe units of 9, which correspond to the pyrrole rings on each side of the carbocyclic moiety, gave (4)J(Me,H) = 0.9-1.0 Hz. These values are in accord with those expected if the exterior carbon-carbon bonds of the pyrrole units next to the indene ring are part of a fully delocalized 18pi electron system, while the C=C bond of the remaining pyrrole ring retains substantial olefinic character.

  DOI：

  10.1021/jo020703u
• 作为产物：
  描述：

  3-甲基-1H-吡咯-2-甲酸乙酯 在 sodium hydroxide 、 溶剂黄146 作用下， 以 乙醇 、 乙二醇 为溶剂， 反应 18.0h， 生成 2,5-bis(5-benzyloxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)-3-methylpyrrole
  参考文献：
  名称：

  Conjugated Macrocycles Related to the Porphyrins. 25. Proton NMR Spectroscopic Evidence for a Preferred [18]Annulene Substructure in Carbaporphyrins from the Magnitude of Selected ⁴J_H,H CHCCH₃ Coupling Constants

  摘要：

  Two new benzocarbaporphyrins with four or five alkyl substituents have been synthesized by the "3 + 1" MacDonald methodology. At lower temperatures, the proton NMR spectrum of the asymmetrically substituted carbaporphyrin 8 gave two NH resonances, while carbaporphyrin 9, which retains a plane of symmetry, gave only one resonance of this kind. As no additional peaks were seen for the remaining protons, these data strongly support the proposal that a single tautomer predominates in solution where the two NH protons flank the interior CH. Carbaporphyrin 8, which has a CH=CMe unit on the pyrrolic ring opposite the indene moiety, gave a long-range coupling constant of (4)J(Me,H) = 1.3-1.4 Hz. On the other hand, the CH=CMe units of 9, which correspond to the pyrrole rings on each side of the carbocyclic moiety, gave (4)J(Me,H) = 0.9-1.0 Hz. These values are in accord with those expected if the exterior carbon-carbon bonds of the pyrrole units next to the indene ring are part of a fully delocalized 18pi electron system, while the C=C bond of the remaining pyrrole ring retains substantial olefinic character.

  DOI：

  10.1021/jo020703u

文献信息

• The Rational Synthesis of Chlorins via Rearrangement of Porphodimethenes:  Influence of β-Substituents on the Regioselectivity and Stereoselectivity of Pyrroline Ring Formation
  作者：Dennis H. Burns、Yue H. Li、Dong C. Shi、Timothy M. Caldwell

  DOI：10.1021/jo020105f

  日期：2002.6.1

  density, with an electron-neutral hydrogen or an electron-withdrawing carbonyl beta-substituent demonstrating the greatest influence on the formation of the pyrroline ring. The synthesis is highly stereoselective when epimerization of the pyrroline ring beta-carbons is possible, furnishing only the trans-reduced sterioisomer. Finally, there is substantial evidence that a fifth, axial ligand is involved

  本文报道的二甲亚砜重排方法提供了从易得的吡咯前体中合理，分步合成二氢卟酚的方法。中间体二氧戊二烯可直接通过“ 2 + 2”麦克唐纳缩合反应，或由三吡喃和双甲酰基吡咯的对称性较小的“ 3 +1”缩合反应提供。合成途径短且高度收敛，特别是在“ 3 +1”方法的情况下，并以良好至中等的产率提供二氢卟酚。合成具有很高的区域选择性，并且似乎基于β取代基稳定过量电子密度的能力，其中电子中性氢或吸电子羰基β取代基对吡咯啉环的形成影响最大。当吡咯啉环β-碳的差向异构化是可能的时，该合成是高度立体选择性的，仅提供反式还原的立体异构体。最终，有充分的证据表明，在pi系统从金属卟啉二甲到金属氯霉素的重排过程中，第五个轴向配体参与了外围氢的移位。