[5-[(5-bromo-1H-pyrrol-2-yl)-[4-(2-trimethylsilylethynyl)phenyl]methyl]-1H-pyrrol-2-yl]-(3,5-ditert-butylphenyl)methanol | 475560-27-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: [5-[(5-bromo-1H-pyrrol-2-yl)-[4-(2-trimethylsilylethynyl)phenyl]methyl]-1H-pyrrol-2-yl]-(3,5-ditert-butylphenyl)methanol
• CAS: 475560-27-1
• 化学式: C₃₅H₄₃BrN₂OSi
• 分子量: 615.729
• InChiKey: GWMROZSEQMGWOC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.19
• 重原子数：
  40
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  51.8
• 氢给体数：
  3
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [5-[(5-bromo-1H-pyrrol-2-yl)-[4-(2-trimethylsilylethynyl)phenyl]methyl]-1H-pyrrol-2-yl]-(3,5-ditert-butylphenyl)methanol 在 2,2,6,6-四甲基哌啶 、 zinc diacetate 、 silver trifluoromethanesulfonate 、 三氟乙酸 作用下， 以 乙腈 为溶剂， 反应 12.5h， 生成 Zn(II)-5-(3,5-di-tert-butylphenyl)-10-(4-ethynylphenyl)-17,18-dihydro-18,18-dimethylporphyrin
  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 3,5-di-tert-butylbenzenecarbothioate 在 sodium tetrahydroborate 、 N-溴代丁二酰亚胺(NBS) 、 乙基溴化镁 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 4.0h， 生成 [5-[(5-bromo-1H-pyrrol-2-yl)-[4-(2-trimethylsilylethynyl)phenyl]methyl]-1H-pyrrol-2-yl]-(3,5-ditert-butylphenyl)methanol
  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

• Probing the Rate of Hole Transfer in Oxidized Synthetic Chlorin Dyads via Site-Specific ¹³C-Labeling
  作者：Elías J. Nieves-Bernier、James R. Diers、Masahiko Taniguchi、Dewey Holten、David F. Bocian、Jonathan S. Lindsey

  DOI：10.1021/jo100527h

  日期：2010.5.21

  analysis of the hyperfine interactions observed in the EPR spectrum of the π-cation radical. This strategy has been previously employed to probe the hole/electron-transfer process in oxidized multiporphyrin arrays of normal isotopic composition, wherein 1H and 14N serve as the hyperfine “clocks”, and in arrays containing site-specific 13C-labels, which serve as additional hyperfine clocks. Herein,

  了解多组分分子体系结构相互作用组成部分之间的电子通信对于在包括人工光合作用和分子电子学在内的各个领域进行合理设计非常重要。检查氧化四吡咯阵列中基态空穴/电子转移的一种策略依赖于对在π阳离子自由基的EPR光谱中观察到的超精细相互作用的分析。先前已采用此策略来探测具有正常同位素组成的氧化多卟啉阵列中的空穴/电子转移过程，其中1 H和14 N作为超精细“钟”，以及包含位点特异性13的阵列C标签，用作额外的超精细时钟。在此，将超精细时钟策略应用于二氢卟啉（二氢卟酚）的二元组。氯霉素比卟啉与叶绿素在结构上更紧密相关。从头合成策略已被用来在二氢卟酚大环的19位引入13 C标记，后者是一个大的电子/空穴密度位点，可从13 C-硝基甲烷开始合成获得。将所得的单独的13 C-标记的二氢卟酚与未标记的二氢卟酚偶联，得到二联体，其中二苯乙炔连接子跨越两个二氢二氢卟酚锌的10位。对自然丰度和13的单阳离子的EPR