(1R,6R,11R,19R)-15-(4-methylphenyl)sulfonyl-2,5,12,15,18-pentazatricyclo[17.4.0.06,11]tricosane-3,13,17-trione | 160884-80-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类
• 英文名称: (1R,6R,11R,19R)-15-(4-methylphenyl)sulfonyl-2,5,12,15,18-pentazatricyclo[17.4.0.06,11]tricosane-3,13,17-trione
• CAS: 160884-80-0
• 化学式: C₂₅H₃₇N₅O₅S
• 分子量: 519.665
• InChiKey: ITDNLTVCTICTKL-GXRSIYKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  36
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  145
• 氢给体数：
  4
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (1R,6R,11R,19R)-15-(4-methylphenyl)sulfonyl-2,5,12,15,18-pentazatricyclo[17.4.0.06,11]tricosane-3,13,17-trione 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 生成 2R,3R,8R,9R-bis(cyclohexano)-1,4,7,10,13-pentaazacyclopentadecane
  参考文献：
  名称：

  通过双（氯乙酰胺）方法制备的新的构象受限的聚氮杂大环

  摘要：

  描述了两个新的一系列构象受限的聚氮杂大环化合物的合成，其特征是在大环环碳上具有多取代基。

  DOI：

  10.1016/s0040-4039(00)75981-8
• 作为产物：
  描述：

  N-对甲苯磺酰甘氨酸 在 N,N-二甲基乙酰胺 作用下， 生成 (1R,6R,11R,19R)-15-(4-methylphenyl)sulfonyl-2,5,12,15,18-pentazatricyclo[17.4.0.06,11]tricosane-3,13,17-trione
  参考文献：
  名称：

  通过双（氯乙酰胺）方法制备的新的构象受限的聚氮杂大环

  摘要：

  描述了两个新的一系列构象受限的聚氮杂大环化合物的合成，其特征是在大环环碳上具有多取代基。

  DOI：

  10.1016/s0040-4039(00)75981-8

文献信息

• New conformationally constrained polyaza macrocycles prepared via the bis(chloroacetamide) method
  作者：Patrick J. Lennon、Hayat Rahman、Karl W. Aston、Susan L. Henke、Dennis P. Riley

  DOI：10.1016/s0040-4039(00)75981-8

  日期：1994.1

  The synthesis of two new series of conformationally constrained polyazamacrocycles featuring polysubstitution at macrocycle ring carbons is described.

  描述了两个新的一系列构象受限的聚氮杂大环化合物的合成，其特征是在大环环碳上具有多取代基。
• Toward the Rational Design of Superoxide Dismutase Mimics:  Mechanistic Studies for the Elucidation of Substituent Effects on the Catalytic Activity of Macrocyclic Manganese(II) Complexes
  作者：Dennis P. Riley、Patrick J. Lennon、William L. Neumann、Randy H. Weiss

  DOI：10.1021/ja964271e

  日期：1997.7.1

  Two new isomeric bis(trans-fused cyclohexano) substituted 1,4,7,10,13-pentaazacyclopentadecane ligands and their Mn(II) complexes, 3 and 14, have been synthesized, and their activity as superoxide dismutase (SOD) catalysts has been studied. Complex 3 is an excellent SOD catalyst with a second-order rate constant at pH 7.4 of 1.2 x 10(+8) M-1 s(-1). In contrast, the isomeric complex 4 has virtually no detectable catalytic SOD activity, implying the need to understand the effect that the position, number, and stereochemistry of substituents exert on the catalytic rate. The crystal structure of the complex 4 was determined and reveals that the Mn(II) ion is coordinated in a pentagonal bipyramid array of the dye nitrogens of the macrocyclic ligand and capped by two trans-chloro ligands. Crystal data for MnC18H37Cl2N5 are as follows: triclinic at 20 degrees C, space group P-1-C(i)2 (no. 2); a = 9.746(3) Angstrom, b = 12.631(6) Angstrom, c = 11.311(5) Angstrom; alpha = 73.14(4)degrees, beta = 76.39(3)degrees, gamma = 79.98(3)degrees, V = 1287(1) Angstrom(3), and Z = 2 (rho(calc) = 1.279 g/cm(3); mu(2) Mo K-alpha = 6.23 mm(-1)). Mechanistic studies with the complex 3 and the pentamethyl susbstituted complex, 5, including D2O rate studies, are reported and are consistent with the existence of two pathways for the rate-determining electron-transfer from Mn(II) to superoxide: (1) hydrogen atom transfer from a bound water on Mn(IP) to HO2. to yield a Mn(III) hydroxo intermediate and (2) the dissociative pathway in which superoxide anion binds to a vacant coordination site on Mn(II) followed by protonation/oxidation to yield a Mn(III)hydroperoxo species. Subsequent reduction of the intermediate Mn(III) with superoxide anion completes the catalytic cycle. Substituent effects on the rates and relative contribution of the two pathways to the overall rate of SOD activity is ascribed to the propensity of the ligand to fold around Mn(II) forming a pseudo-octahedral complex similar in geometry to the oxidized Mn(III) complex. Folding of the pentaaza macrocyclic ligand is confirmed as a relevant structural motif for this series of Mn(TI) complexes by the X-ray structure determination of the bis(nitrate) derivative of 1, [Mn(C10H25N5)NO3]NO3, which reveals a six-coordinate structure with a folded conformation of the macrocyclic ligand. Crystal data for [Mn(C10H25N5)NO3]NO3: orthorhombic at -100 degrees C, space group P2(1)2(1)2(1); a = 9.457(2) Angstrom, b = 12.758(2) Angstrom, c = 13.834(2) Angstrom, V = 1669.1(5) Angstrom(3), and Z = 4 (rho(calc) = 1.549 g/cm(3)).