19-bromo-2,3,4,5-tetrahydro-1,3,3-trimethyl-10-(4-methylphenyl)-15-[4-[2-(trimethylsilyl)ethoxycarbonyl]phenyl]bilene-a | 378751-02-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: 19-bromo-2,3,4,5-tetrahydro-1,3,3-trimethyl-10-(4-methylphenyl)-15-[4-[2-(trimethylsilyl)ethoxycarbonyl]phenyl]bilene-a
• 英文别名: 2-trimethylsilylethyl 4-[(5-bromo-1H-pyrrol-2-yl)-[5-[(4-methylphenyl)-[5-[(3,3,5-trimethyl-2,4-dihydropyrrol-2-yl)methyl]-1H-pyrrol-2-yl]methyl]-1H-pyrrol-2-yl]methyl]benzoate
• CAS: 378751-02-1
• 化学式: C₄₁H₄₉BrN₄O₂Si
• 分子量: 737.855
• InChiKey: BWFKNZYHKUWAHV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.4
• 重原子数：
  49
• 可旋转键数：
  13
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  86
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  19-bromo-2,3,4,5-tetrahydro-1,3,3-trimethyl-10-(4-methylphenyl)-15-[4-[2-(trimethylsilyl)ethoxycarbonyl]phenyl]bilene-a 在 2,2,6,6-四甲基哌啶 、 zinc diacetate 、 silver trifluoromethanesulfonate 作用下， 以 乙腈 为溶剂， 反应 14.0h， 以41%的产率得到Zn(II)-17,18-dihydro-18,18-dimethyl-5-(4-methylphenyl)-10-[4-[2-(trimethylsilyl)ethoxycarbonyl]phenyl]porphyrin
  参考文献：
  名称：

  Synthesis of Meso-Substituted Chlorins via Tetrahydrobilene-a Intermediates

  摘要：

  Chlorin building blocks incorporating a geminal dimethyl group in the reduced ring and synthetic handles in specific patterns at the perimeter of the macrocycle are expected to have utility in biomimetic and materials chemistry. A prior route employed condensation of a dihydrodipyrrin (Western half) and a bromodipyrromethane-monocarbinol (Eastern half), followed by oxidative cyclization of the putative dihydrobilene-alpha to form the meso-substituted zinc chlorin in yields of similar to 10%. The limited stability of the dihydrodipyrrin precluded study of the chlorin-forming process. We now have refined this methodology. A tetrahydrodipyrrin Western half (2,3,4,5-tetrahydro-1,3,3-trimethyldipyrrin) has been synthesized and found to be quite stable. The condensation of the Western half and an Eastern half (100 mM each) proceeded smoothly in CH3CN containing 100 mM TFA at room temperature for 30 min. The resulting linear tetrapyrrole, a 2,3,4,5-tetrahydrobilene-alpha, also is quite stable, enabling study of the conversion to chlorin. Refined conditions for the oxidative cyclization were found to include the following: the tetrahydrobilene-alpha (10 mM), AgTf (3-5 molar equiv), Zn(OAc)(2) (15 molar equiv), and 2,2,6,6-tetramethylpiperidine (15 molar equiv) in CH3CN at reflux exposed to air for 4-6 h, affording the zinc chlorin. The chlorin-forming process could be implemented in either a two-flask process or a one-flask process. The two-flask process was applied to form six zinc chlorins bearing substituents such as pentafluorophenyl, 3,5-di-tert-butylphenyl, TMS-ethyl benzoate, iodophenyl, or ethynylphenyl (deprotection of the TMS-ethynyl group occurred during the oxidative cyclization process). The stepwise yields (isolated) for the condensation and oxidative cyclization processes forming the tetrahydrobilene and zinc chlorin were 32-72% and 27-62%, respectively, giving overall yields of zinc chlorin from the Eastern and Western halves of 12-45%. Taken together, the refinements introduced enable 100-mg quantities of chlorin building blocks to be prepared in a facile and rational manner.

  DOI：

  10.1021/jo0104835
• 作为产物：
  描述：

  S-2-pyridyl 4-methylbenzothiolate 在 sodium tetrahydroborate 、 N-溴代丁二酰亚胺(NBS) 、 乙基溴化镁 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 乙腈 为溶剂， 反应 4.5h， 生成 19-bromo-2,3,4,5-tetrahydro-1,3,3-trimethyl-10-(4-methylphenyl)-15-[4-[2-(trimethylsilyl)ethoxycarbonyl]phenyl]bilene-a
  参考文献：
  名称：

  Synthesis of Meso-Substituted Chlorins via Tetrahydrobilene-a Intermediates

  摘要：

  Chlorin building blocks incorporating a geminal dimethyl group in the reduced ring and synthetic handles in specific patterns at the perimeter of the macrocycle are expected to have utility in biomimetic and materials chemistry. A prior route employed condensation of a dihydrodipyrrin (Western half) and a bromodipyrromethane-monocarbinol (Eastern half), followed by oxidative cyclization of the putative dihydrobilene-alpha to form the meso-substituted zinc chlorin in yields of similar to 10%. The limited stability of the dihydrodipyrrin precluded study of the chlorin-forming process. We now have refined this methodology. A tetrahydrodipyrrin Western half (2,3,4,5-tetrahydro-1,3,3-trimethyldipyrrin) has been synthesized and found to be quite stable. The condensation of the Western half and an Eastern half (100 mM each) proceeded smoothly in CH3CN containing 100 mM TFA at room temperature for 30 min. The resulting linear tetrapyrrole, a 2,3,4,5-tetrahydrobilene-alpha, also is quite stable, enabling study of the conversion to chlorin. Refined conditions for the oxidative cyclization were found to include the following: the tetrahydrobilene-alpha (10 mM), AgTf (3-5 molar equiv), Zn(OAc)(2) (15 molar equiv), and 2,2,6,6-tetramethylpiperidine (15 molar equiv) in CH3CN at reflux exposed to air for 4-6 h, affording the zinc chlorin. The chlorin-forming process could be implemented in either a two-flask process or a one-flask process. The two-flask process was applied to form six zinc chlorins bearing substituents such as pentafluorophenyl, 3,5-di-tert-butylphenyl, TMS-ethyl benzoate, iodophenyl, or ethynylphenyl (deprotection of the TMS-ethynyl group occurred during the oxidative cyclization process). The stepwise yields (isolated) for the condensation and oxidative cyclization processes forming the tetrahydrobilene and zinc chlorin were 32-72% and 27-62%, respectively, giving overall yields of zinc chlorin from the Eastern and Western halves of 12-45%. Taken together, the refinements introduced enable 100-mg quantities of chlorin building blocks to be prepared in a facile and rational manner.

  DOI：

  10.1021/jo0104835

文献信息

• Synthesis of Meso-Substituted Chlorins via Tetrahydrobilene-<i>a</i> Intermediates
  作者：Masahiko Taniguchi、Doyoung Ra、Guoning Mo、Thiagarajan Balasubramanian、Jonathan S. Lindsey

  DOI：10.1021/jo0104835

  日期：2001.11.1

  Chlorin building blocks incorporating a geminal dimethyl group in the reduced ring and synthetic handles in specific patterns at the perimeter of the macrocycle are expected to have utility in biomimetic and materials chemistry. A prior route employed condensation of a dihydrodipyrrin (Western half) and a bromodipyrromethane-monocarbinol (Eastern half), followed by oxidative cyclization of the putative dihydrobilene-alpha to form the meso-substituted zinc chlorin in yields of similar to 10%. The limited stability of the dihydrodipyrrin precluded study of the chlorin-forming process. We now have refined this methodology. A tetrahydrodipyrrin Western half (2,3,4,5-tetrahydro-1,3,3-trimethyldipyrrin) has been synthesized and found to be quite stable. The condensation of the Western half and an Eastern half (100 mM each) proceeded smoothly in CH3CN containing 100 mM TFA at room temperature for 30 min. The resulting linear tetrapyrrole, a 2,3,4,5-tetrahydrobilene-alpha, also is quite stable, enabling study of the conversion to chlorin. Refined conditions for the oxidative cyclization were found to include the following: the tetrahydrobilene-alpha (10 mM), AgTf (3-5 molar equiv), Zn(OAc)(2) (15 molar equiv), and 2,2,6,6-tetramethylpiperidine (15 molar equiv) in CH3CN at reflux exposed to air for 4-6 h, affording the zinc chlorin. The chlorin-forming process could be implemented in either a two-flask process or a one-flask process. The two-flask process was applied to form six zinc chlorins bearing substituents such as pentafluorophenyl, 3,5-di-tert-butylphenyl, TMS-ethyl benzoate, iodophenyl, or ethynylphenyl (deprotection of the TMS-ethynyl group occurred during the oxidative cyclization process). The stepwise yields (isolated) for the condensation and oxidative cyclization processes forming the tetrahydrobilene and zinc chlorin were 32-72% and 27-62%, respectively, giving overall yields of zinc chlorin from the Eastern and Western halves of 12-45%. Taken together, the refinements introduced enable 100-mg quantities of chlorin building blocks to be prepared in a facile and rational manner.