10-(9-borabicyclo[3.3.1]non-9-yl)-1-(4-bromobenzoyl)-5-[4-(2-trimethylsilyl)ethynylphenyl]dipyrromethane | 816454-74-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 10-(9-borabicyclo[3.3.1]non-9-yl)-1-(4-bromobenzoyl)-5-[4-(2-trimethylsilyl)ethynylphenyl]dipyrromethane
• 英文别名: [1-(9-borabicyclo[3.3.1]nonan-9-yl)-5-[1H-pyrrol-2-yl-[4-(2-trimethylsilylethynyl)phenyl]methyl]pyrrol-2-yl]-(4-bromophenyl)methanone
• CAS: 816454-74-7
• 化学式: C₃₅H₃₈BBrN₂OSi
• 分子量: 621.5
• InChiKey: LRCBGBHFNPJNCU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.17
• 重原子数：
  41
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  37.8
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-碘苯甲酰氯 、 10-(9-borabicyclo[3.3.1]non-9-yl)-1-(4-bromobenzoyl)-5-[4-(2-trimethylsilyl)ethynylphenyl]dipyrromethane 在 magnesium,1,3,5-trimethylbenzene-6-ide,bromide 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 以69%的产率得到[5-[[1-(9-borabicyclo[3.3.1]nonan-9-yl)-5-(4-bromobenzoyl)pyrrol-2-yl]-[4-(2-trimethylsilylethynyl)phenyl]methyl]-1H-pyrrol-2-yl]-(4-iodophenyl)methanone
  参考文献：
  名称：

  9-Acylation of 1-Acyldipyrromethanes Containing a Dialkylboron Mask for the α-Acylpyrrole Motif

  摘要：

  1,9-Diacyldipyrromethanes are important precursors to porphyrins, yet synthetic access remains limited owing to (1) poor conversion in the 9-acylation of 1-acyldipyrromethanes and (2) handling difficulties because acy1dipyrromethanes typically streak upon chromatography and give amorphous powders upon attempted crystallization. A reliable means for converting a dipyrromethane to a 1-acyldipyrromethane-dialkylboron complex was recently developed, where the dialkylboron (BR2) unit renders the complex hydrophobic and thereby facilitates isolation. Herein a refined preparation of 1,9-diacyldipyrromethanes is presented that employs the 1-acyldipyrromethane-BR2 complex as a substrate for 9-acylation. The dialkylboron unit provides protection for the alpha-acylpyrrole unit. 9-Acylation requires formation of the pyrrolyl-MgBr reagent and the presence of 1 equiv of a nonnucleophilic base to quench the proton liberated upon alpha-acylation. Reaction of the 1-acyldipyrromethane-BR2 complex (1 equiv) with mesitylmagnesium. bromide (2 equiv) followed by the addition of an acylating agent (S-2-pyridyl thioate or acid chloride, 1.1 equiv) gives the corresponding 1,9-diacyldipyrromethane-BR2 complex. The acylation method afforded 1,9-diacyldipyrromethaneBR(2) complexes with limited or no chromatography in yields of 64-92%. The 1,9-diacyldipyrromethane-BR2 complexes are stable to routine handling, are readily soluble in common organic solvents, crystallize readily, and can now be prepared in multigram quantities through use of stoichiometric quantities of reagents.

  DOI：

  10.1021/jo048587d
• 作为产物：
  描述：

  4-三甲基硅乙炔基苯甲醛 在 indium(III) chloride 、 乙基溴化镁 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 3.09h， 生成 10-(9-borabicyclo[3.3.1]non-9-yl)-1-(4-bromobenzoyl)-5-[4-(2-trimethylsilyl)ethynylphenyl]dipyrromethane
  参考文献：
  名称：

  Boron-Complexation Strategy for Use with 1-Acyldipyrromethanes

  摘要：

  1-Acyldipyrromethanes are important precursors in rational syntheses of diverse porphyrinic compounds. 1-Acyldipyrromethanes are difficult to purify, typically streaking upon chromatography and giving amorphous powders upon attempted crystallization. A solution to this problem has been achieved by reacting the 1-acyldipyrromethane with a dialkylboron triflate (e.g., Bu2B-OTf or 9-BBN-OTf) to give the corresponding B,B-dialkyl-B-(1-acyldipyrromethane)boron(III) complex. The reaction is selective for a 1-acyldipyrromethane in the presence of a dipyrromethane. The 1-acyldipyrromethane-boron complexes are stable to routine handling, are soluble in common organic solvents, are hydrophobic, crystallize readily, and chromatograph without streaking. The 1-acyldipyrromethane can be liberated in high yield from the boron complex upon treatment with 1-pentanol. Alternatively, the 1-acyldipyrromethane-boron complex can be used in the formation of a trans-A(2)B(2)-porphyrin. In summary, the boron-complexation strategy has broad scope and greatly facilitates the isolation of 1-acyldipyrromethanes.

  DOI：

  10.1021/jo0492620

文献信息

• Boron-Complexation Strategy for Use with 1-Acyldipyrromethanes
  作者：Kannan Muthukumaran、Marcin Ptaszek、Bruce Noll、W. Robert Scheidt、Jonathan S. Lindsey

  DOI：10.1021/jo0492620

  日期：2004.8.1

  1-Acyldipyrromethanes are important precursors in rational syntheses of diverse porphyrinic compounds. 1-Acyldipyrromethanes are difficult to purify, typically streaking upon chromatography and giving amorphous powders upon attempted crystallization. A solution to this problem has been achieved by reacting the 1-acyldipyrromethane with a dialkylboron triflate (e.g., Bu2B-OTf or 9-BBN-OTf) to give the corresponding B,B-dialkyl-B-(1-acyldipyrromethane)boron(III) complex. The reaction is selective for a 1-acyldipyrromethane in the presence of a dipyrromethane. The 1-acyldipyrromethane-boron complexes are stable to routine handling, are soluble in common organic solvents, are hydrophobic, crystallize readily, and chromatograph without streaking. The 1-acyldipyrromethane can be liberated in high yield from the boron complex upon treatment with 1-pentanol. Alternatively, the 1-acyldipyrromethane-boron complex can be used in the formation of a trans-A(2)B(2)-porphyrin. In summary, the boron-complexation strategy has broad scope and greatly facilitates the isolation of 1-acyldipyrromethanes.
• 9-Acylation of 1-Acyldipyrromethanes Containing a Dialkylboron Mask for the α-Acylpyrrole Motif
  作者：Syeda Huma H. Zaidi、Kannan Muthukumaran、Shun-ichi Tamaru、Jonathan S. Lindsey

  DOI：10.1021/jo048587d

  日期：2004.11.1

  1,9-Diacyldipyrromethanes are important precursors to porphyrins, yet synthetic access remains limited owing to (1) poor conversion in the 9-acylation of 1-acyldipyrromethanes and (2) handling difficulties because acy1dipyrromethanes typically streak upon chromatography and give amorphous powders upon attempted crystallization. A reliable means for converting a dipyrromethane to a 1-acyldipyrromethane-dialkylboron complex was recently developed, where the dialkylboron (BR2) unit renders the complex hydrophobic and thereby facilitates isolation. Herein a refined preparation of 1,9-diacyldipyrromethanes is presented that employs the 1-acyldipyrromethane-BR2 complex as a substrate for 9-acylation. The dialkylboron unit provides protection for the alpha-acylpyrrole unit. 9-Acylation requires formation of the pyrrolyl-MgBr reagent and the presence of 1 equiv of a nonnucleophilic base to quench the proton liberated upon alpha-acylation. Reaction of the 1-acyldipyrromethane-BR2 complex (1 equiv) with mesitylmagnesium. bromide (2 equiv) followed by the addition of an acylating agent (S-2-pyridyl thioate or acid chloride, 1.1 equiv) gives the corresponding 1,9-diacyldipyrromethane-BR2 complex. The acylation method afforded 1,9-diacyldipyrromethaneBR(2) complexes with limited or no chromatography in yields of 64-92%. The 1,9-diacyldipyrromethane-BR2 complexes are stable to routine handling, are readily soluble in common organic solvents, crystallize readily, and can now be prepared in multigram quantities through use of stoichiometric quantities of reagents.