benzyl 3-ethyl-4'-(2-methoxycarbonylethyl)-3',4-dimethyl-5'-t-butoxycarbonylpyrromethane-5-carboxylate | 64271-04-1

• 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: benzyl 3-ethyl-4'-(2-methoxycarbonylethyl)-3',4-dimethyl-5'-t-butoxycarbonylpyrromethane-5-carboxylate
• 英文别名: tert-butyl 5'-(benzyloxycarbonyl)-3'-ethyl-4-(2-methoxycarbonylethyl)-3,4'-dimethyl-2,2'-dipyrrylmethane-5-carboxylate；5'-Benzyloxycarbonyl-5-tert-butoxycarbonyl-3'-aethyl-4-(2-methoxycarbonylaethyl)-3,4'-dimethyl-dipyrrolylmethan；4-ethyl-3'-(2-methoxycarbonyl-ethyl)-3,4'-dimethyl-5,5'-methanediyl-bis-pyrrole-2-carboxylic acid 2-benzyl ester 2'-tert-butyl ester；benzyl 4-ethyl-5-[[4-(3-methoxy-3-oxopropyl)-3-methyl-5-[(2-methylpropan-2-yl)oxycarbonyl]-1H-pyrrol-2-yl]methyl]-3-methyl-1H-pyrrole-2-carboxylate
• CAS: 64271-04-1
• 化学式: C₃₀H₃₈N₂O₆
• 分子量: 522.642
• InChiKey: YZFADLVCYRCDCU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  38
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  111
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  benzyl 3-ethyl-4'-(2-methoxycarbonylethyl)-3',4-dimethyl-5'-t-butoxycarbonylpyrromethane-5-carboxylate 在 palladium on activated charcoal 氢气 、 三乙胺 作用下， 以 甲醇 为溶剂， 反应 14.0h， 以97%的产率得到5'-(tert-butoxycarbonyl)-3-ethyl-4'-(2-methoxycarbonylethyl)-3',4-dimethyl-2,2'-dipyrrylmethane-5-carboxylic acid
  参考文献：
  名称：

  Normal and Abnormal Heme Biosynthesis. 1. Synthesis and Metabolism of Di- and Monocarboxylic Porphyrinogens Related to Coproporphyrinogen-III and Harderoporphyrinogen:  A Model for the Active Site of Coproporphyrinogen Oxidase

  摘要：

  Coproporphyrinogen oxidase (copro'gen oxidase), which catalyses the conversion of coproporphyrinogen-III via a monovinylic intermediate to protoporphyrinogen-IX, is one of the least well understood enzymes in the heme biosynthetic pathway. To develop a model for the substrate recognition and binding recognition for this enzyme, a series of substrate analogues were prepared with two alkyl substituents on positions 13 and 17 in place of the usual propionate residues. Although the required substrate probes are porphyrinogens (hexahydroporphyrins), the corresponding porphyrin methyl esters were initialy synthesized via a,c-biladiene intermediates. These were hydrolyzed and reduced with 3% sodium amalgam to give the unstable porphyrinogens needed for the biochemical investigations. These modified structures were metabolized by avian preparations of copro'gen oxidase to give monovinylic products, but the second propionate residue was not further metabolized. In three cases, the metabolites were isolated and further characterized by proton NMR spectroscopy and mass spectrometry. When methyl or ethyl groups were placed at the 13 and 17 positions, the resulting porphyrinogens were very good substrates (although the ethyl version, mesoporphyrinogen-VI, gave slightly better results), but when propyl units were introduced metabolism was significantly inhibited and the butyl-substituted structure was only slightly transformed after long incubation periods. These results suggest the presence of an active-site lipophobic region near the catalytic site for copro'gen oxidase. The observation that the related 3-vinyl- and 3-ethylporphyrinogens with 13,17-diethyl substituents were not substrates for this enzyme confirmed the need for a second propionate residue to hold the substrate in place at the catalytic site.

  DOI：

  10.1021/jo981473f
• 作为产物：
  描述：

  t-butyl 5-iodo-3-(2-methoxycarbonylethyl)-4-methylpyrrole-2-carboxylate 在 platinum(IV) oxide 氢气 、 sodium acetate 、 对甲苯磺酸 作用下， 以 甲醇 、 溶剂黄146 为溶剂， 20.0~40.0 ℃ 、101.33 kPa 条件下， 反应 10.0h， 生成 benzyl 3-ethyl-4'-(2-methoxycarbonylethyl)-3',4-dimethyl-5'-t-butoxycarbonylpyrromethane-5-carboxylate
  参考文献：
  名称：

  卟啉的合成和生物合成研究。第9部分。异卟啉，脱氢异卟啉和脱乙基异卟啉的合成

  摘要：

  标题化合物，其通过从皮肤卟啉症或迟发性与六氯苯中毒大鼠的患者排出已经由合成b -oxobilane路线。由对应于大环的DA和BC环的吡咯甲烷制备异卟啉四甲酯（7a），以类似方式制备脱乙基类似物（7b）。后者的乙酰化，然后还原和脱水，然后得到脱氢异卟啉四甲基酯（7d）。合成中产生的少量副产物已显示是通过BC吡咯甲烷的重排而产生的。

  DOI：

  10.1039/p19870000287

文献信息

• Normal and Abnormal Heme Biosynthesis. 1. Synthesis and Metabolism of Di- and Monocarboxylic Porphyrinogens Related to Coproporphyrinogen-III and Harderoporphyrinogen:  A Model for the Active Site of Coproporphyrinogen Oxidase
  作者：Timothy D. Lash、Ukti N. Mani、Martin A. Drinan、Chun Zhen、Troii Hall、Marjorie A. Jones

  DOI：10.1021/jo981473f

  日期：1999.1.1

  Coproporphyrinogen oxidase (copro'gen oxidase), which catalyses the conversion of coproporphyrinogen-III via a monovinylic intermediate to protoporphyrinogen-IX, is one of the least well understood enzymes in the heme biosynthetic pathway. To develop a model for the substrate recognition and binding recognition for this enzyme, a series of substrate analogues were prepared with two alkyl substituents on positions 13 and 17 in place of the usual propionate residues. Although the required substrate probes are porphyrinogens (hexahydroporphyrins), the corresponding porphyrin methyl esters were initialy synthesized via a,c-biladiene intermediates. These were hydrolyzed and reduced with 3% sodium amalgam to give the unstable porphyrinogens needed for the biochemical investigations. These modified structures were metabolized by avian preparations of copro'gen oxidase to give monovinylic products, but the second propionate residue was not further metabolized. In three cases, the metabolites were isolated and further characterized by proton NMR spectroscopy and mass spectrometry. When methyl or ethyl groups were placed at the 13 and 17 positions, the resulting porphyrinogens were very good substrates (although the ethyl version, mesoporphyrinogen-VI, gave slightly better results), but when propyl units were introduced metabolism was significantly inhibited and the butyl-substituted structure was only slightly transformed after long incubation periods. These results suggest the presence of an active-site lipophobic region near the catalytic site for copro'gen oxidase. The observation that the related 3-vinyl- and 3-ethylporphyrinogens with 13,17-diethyl substituents were not substrates for this enzyme confirmed the need for a second propionate residue to hold the substrate in place at the catalytic site.
• Synthetic and biosynthetic studies of porphyrins. Part 9. Synthesis of isocoproporphyrin, dehydroisocoproporphyrin, and de-ethylisocoproporphyrin
  作者：Anthony H. Jackson、Timothy D. Lash、David J. Ryder

  DOI：10.1039/p19870000287

  日期：——

  The title compounds, which were excreted by patients suffering from porphyria cutanea tarda or rats poisoned with hexachlorobenzene have been synthesized by the b-oxobilane route. Isocoproporphyrin tetramethyl ester (7a) was prepared from pyrromethanes corresponding to rings DA and BC of the macrocycle, and the de-ethyl analogue (7b) was prepared in a similar fashion; acetylation of the latter followed

  标题化合物，其通过从皮肤卟啉症或迟发性与六氯苯中毒大鼠的患者排出已经由合成b -oxobilane路线。由对应于大环的DA和BC环的吡咯甲烷制备异卟啉四甲酯（7a），以类似方式制备脱乙基类似物（7b）。后者的乙酰化，然后还原和脱水，然后得到脱氢异卟啉四甲基酯（7d）。合成中产生的少量副产物已显示是通过BC吡咯甲烷的重排而产生的。