N-benzoyl bis(pyridin-2-yl)methylamine

• 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: N-benzoyl bis(pyridin-2-yl)methylamine
• 英文别名: N-[bis(pyridin-2-yl)methyl]benzamide；(di(2-pyridyl)methyl)benzamide；N-benzoylbis(pyridin-2-yl)methylamine；bpmbaH；Bis(2 pyridyl)methyl benzamide；N-(dipyridin-2-ylmethyl)benzamide
• 化学式: C₁₈H₁₅N₃O
• 分子量: 289.337
• InChiKey: QGPCGPPFCGYVRO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  54.9
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-benzoyl bis(pyridin-2-yl)methylamine 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 生成 Re(CO)3(N-[bis(pyridin-2-yl)methyl]benzamide)*MeCN
  参考文献：
  名称：

  Studies of the reactions of tripodal pyridine-containing ligands with Re(CO)5Br leading to rheniumtricarbonyl complexes with potential biomedical applications

  摘要：

  N-酰化三-(吡啶-2-基)甲胺(LH)与[Re(CO)5Br]反应形成的配合物取决于配体的结构和反应条件。因此，虽然 N-[1,1,1-三-(吡啶-2-基)甲基]乙酰胺通过三个吡啶氮配位得到稳定的阳离子络合物 [LHRe(CO)3Br]，但类似的 N-苯甲酰基配体在类似条件下反应，得到中性配合物 [LRe(CO)3]，通过两个吡啶氮和去质子化酰胺进行配位。为了尝试解释这些不同的结果，我们研究了一些结构相关的 N-酰化 [1,1-双(吡啶-2-基)]甲胺 (L′H) 与 [Re(CO)5Br] 的反应，并研究了确定的反应途径。这些研究表明，最初形成中性络合物 [L'HRe(CO)3Br]，其中配体的酰胺部分不配位，但该络合物在适当的条件下会重新排列，得到阳离子络合物 [L'HRe(CO) )3]Br，其中配位酰胺氮要么保持质子化，要么以其亚氨酸互变异构形式存在。通过加热或在碱存在下从这些络合物中消除 HBr，然后得到稳定的中性络合物 [L'Re(CO)3]。 N-酰基和三足配体 (L''H) 顶端的任何取代基对反应途径中中间体配合物的相对稳定性的影响有助于解释所观察到的 N-酰化基团的行为差异。三(吡啶-2-基)甲胺(LH)。

  DOI：

  10.1039/c1dt11020a
• 作为产物：
  描述：

  苯甲酰氯 、 1,1-双(吡啶-2-基)甲胺 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以75%的产率得到N-benzoyl bis(pyridin-2-yl)methylamine
  参考文献：
  名称：

  Iron-Catalyzed Olefin cis-Dihydroxylation Using a Bio-Inspired N,N,O-Ligand

  摘要：

  Nature has evolved enzymes that carry out the cis-dihydroxylation of C=C bonds in the biodegradation of arenes in the environment. These enzymes, called Rieske dioxygenases, have mononuclear iron centers coordinated to a 2-His-1-carboxylate facial triad motif that has emerged as a common structural element among many nonheme iron enzymes. In contrast, olefin cis-dihydroxylation is conveniently carried out by OsO4 and related species in synthetic procedures. To develop more environmentally benign strategies for carrying out these transformations, we have designed Ph-DPAH [(di-(2-pyridyl)methyl)benzamide], a tridentate ligand that mimics the facial N,N,O site of the mononuclear iron center in the Rieske dioxygenases. Its iron(II) complex has been found to catalyze olefin cis-dihydroxylation almost exclusively and with high H2O2 conversion efficiency on a wide range of substrates. and 18O labeling experiments suggest the participation of an FeV oxidant.

  DOI：

  10.1021/ja054947i

文献信息

• Iron-Catalyzed Olefin <i>cis</i>-Dihydroxylation Using a Bio-Inspired <i>N</i>,<i>N</i>,<i>O</i>-Ligand
  作者：Paul D. Oldenburg、Albert A. Shteinman、Lawrence Que

  DOI：10.1021/ja054947i

  日期：2005.11.1

  Nature has evolved enzymes that carry out the cis-dihydroxylation of C=C bonds in the biodegradation of arenes in the environment. These enzymes, called Rieske dioxygenases, have mononuclear iron centers coordinated to a 2-His-1-carboxylate facial triad motif that has emerged as a common structural element among many nonheme iron enzymes. In contrast, olefin cis-dihydroxylation is conveniently carried out by OsO4 and related species in synthetic procedures. To develop more environmentally benign strategies for carrying out these transformations, we have designed Ph-DPAH [(di-(2-pyridyl)methyl)benzamide], a tridentate ligand that mimics the facial N,N,O site of the mononuclear iron center in the Rieske dioxygenases. Its iron(II) complex has been found to catalyze olefin cis-dihydroxylation almost exclusively and with high H2O2 conversion efficiency on a wide range of substrates. and 18O labeling experiments suggest the participation of an FeV oxidant.
• Studies of rheniumtricarbonyl complexes of tripodal pyridyl-based ligands
  作者：D. Vaughan Griffiths、Mohamad J. Al-Jeboori、Phillip J. Arnold、Yuen-Ki Cheong、Philip Duncanson、Majid Motevalli

  DOI：10.1016/j.ica.2009.11.039

  日期：2010.4

  The reaction of N-benzoyl and N-acetyl tris(pyridin-2-yl) methylamine 1b and 1c (LH = tpmbaH and tpmaaH) with [Re(CO)(5)Br] has been investigated and shown to proceed via the initial formation of a cationic rheniumtricarbonyl complex [(LH)Re(CO)(3)]Br in which coordination of the ligand occurs via the three pyridine rings. For tpmbaH 1b, but not tpmaaH 1c, this initial complex 2b readily undergoes the loss of HBr to give a neutral octahedral complex 4b [(L)Re(CO)(3)] where coordination occurs via two of the pyridine rings and the deprotonated amide nitrogen. The H-1 NMR spectrum of the latter complex 4b is very unusual in that at room temperature the signals for the 3-H protons on the coordinated pyridine rings are not visible due to extreme broadening of these resonances. Comparison with the analogous complex 7 from N-benzoyl bis(pyridin-2-yl) methylamine 6b (bpmbaH) confirms that this is due to rotation of the uncoordinated pyridine ring. The structure of the cationic complex 3d [(LH)Re(CO)(3)]Br formed from N-benzyl tris(pyridin-2-yl) methylamine 1d (bz-tpmaH) is also discussed. The crystal structures of complexes [(tpmba)Re(CO)(3)] 4b, [(bz-tpmaH)Re(CO)(3)]Br 3d and [(bpmba)Re(CO)(3)] 7 have been determined. In all complexes the coordination geometry around Re is distorted octahedral with a facRe(CO)(3)}(+) core. (C) 2009 Elsevier B.V. All rights reserved.
• Studies of the reactions of tripodal pyridine-containing ligands with Re(CO)5Br leading to rheniumtricarbonyl complexes with potential biomedical applications
  作者：D. Vaughan Griffiths、Yuen-Ki Cheong、Philip Duncanson、Majid Motevalli

  DOI：10.1039/c1dt11020a

  日期：——

  The complexes formed from the reaction of N-acylated tris-(pyridin-2-yl)methylamine (LH) with [Re(CO)5Br] depend on the structure of the ligand and the reaction conditions. Thus, while N-[1,1,1-tris-(pyridin-2-yl)methyl]acetamide coordinates through the three pyridine nitrogens to give a stable cationic complex [LHRe(CO)3Br], the analogous N-benzoyl ligand reacts under similar conditions to give a neutral complex [LRe(CO)3] with coordination through two pyridine nitrogens and a deprotonated amide. To try to explain these different outcomes, the reactions of some structurally related N-acylated [1,1-bis(pyridin-2-yl)]methylamines (L′H) with [Re(CO)5Br] have been studied and the reaction pathways identified. These studies indicate that a neutral complex [L′HRe(CO)3Br] is initially formed in which the amide portion of the ligand is uncoordinated, but that this complex under appropriate conditions then rearranges to give a cationic complex [L′HRe(CO)3]Br in which the coordinated amide nitrogen either remains protonated or is present in its imidic acid tautomeric form. Elimination of HBr from these complexes either thermally or in the presence of base then gives stable neutral complexes [L′Re(CO)3]. The impact of the N-acyl group and any substituent at the apex of the tripodal ligands (L′′H) on the relative stabilities of intermediate complexes on the reaction pathway helps provide an explanation for the observed difference in behaviour of the N-acylated tris(pyridin-2-yl)methylamines (LH).

  N-酰化三-(吡啶-2-基)甲胺(LH)与[Re(CO)5Br]反应形成的配合物取决于配体的结构和反应条件。因此，虽然 N-[1,1,1-三-(吡啶-2-基)甲基]乙酰胺通过三个吡啶氮配位得到稳定的阳离子络合物 [LHRe(CO)3Br]，但类似的 N-苯甲酰基配体在类似条件下反应，得到中性配合物 [LRe(CO)3]，通过两个吡啶氮和去质子化酰胺进行配位。为了尝试解释这些不同的结果，我们研究了一些结构相关的 N-酰化 [1,1-双(吡啶-2-基)]甲胺 (L′H) 与 [Re(CO)5Br] 的反应，并研究了确定的反应途径。这些研究表明，最初形成中性络合物 [L'HRe(CO)3Br]，其中配体的酰胺部分不配位，但该络合物在适当的条件下会重新排列，得到阳离子络合物 [L'HRe(CO) )3]Br，其中配位酰胺氮要么保持质子化，要么以其亚氨酸互变异构形式存在。通过加热或在碱存在下从这些络合物中消除 HBr，然后得到稳定的中性络合物 [L'Re(CO)3]。 N-酰基和三足配体 (L''H) 顶端的任何取代基对反应途径中中间体配合物的相对稳定性的影响有助于解释所观察到的 N-酰化基团的行为差异。三(吡啶-2-基)甲胺(LH)。