2-[4-(methylamino)-3-pyridyl]ethan-1-ol | 257937-14-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2-[4-(methylamino)-3-pyridyl]ethan-1-ol
• 英文别名: 2-[4-(Methylamino)pyridin-3-yl]ethanol
• CAS: 257937-14-7
• 化学式: C₈H₁₂N₂O
• mdl: MFCD18802425
• 分子量: 152.196
• InChiKey: SNEIPYNUUXTHHJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.375
• 拓扑面积：
  45.2
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-[4-(methylamino)-3-pyridyl]ethan-1-ol 在 N-溴代丁二酰亚胺(NBS) 、 (N-methylphenylamino)triphenylphosphonium iodide 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 生成 7-bromo-1-methyl-2-pyrrolino[3,2-c]pyridine
  参考文献：
  名称：

  Configurationally Stable Biaryl Analogues of 4-(Dimethylamino)pyridine:  A Novel Class of Chiral Nucleophilic Catalysts

  摘要：

  A short synthetic approach toward a novel class of chiral nucleophilic catalysts, the dissymmetry of which stems from restricted rotation about an Ar-Ar bond, has been developed. The key steps of the synthesis include preparation of a nucleophilic 1-methyl-2-pyrrolino[3,2-c]pyridine core 16 by ortho-lithiation and creation of the biaryl axes via Suzuki cross-coupling reactions. Comparative HPLC studies of racemization for configurationally labile biaryls 31, 38, and 43 containing 1-methyl-2-pyrrolino[3,2-c]pyridine, 4-(dimethylamino)pyridine, and 4-(1-pyrrolidino)pyridine cores, respectively, have demonstrated that a pyrrolidino substituent ortho to the biaryl axis is optimal for slowing Ar-Ar rotation. Biaryls containing all three cores have been shown to retain DMAP-like catalytic activity in the acylation of a hindered alcohol. Biaryls 55 and 56, which are configurationally stable at ambient temperature, have also been prepared via modification of configurationally labile derivatives. Compounds 55 and 56 in optically pure form should provide a useful starting point for studies on catalytic asymmetric acyl transfer using atropisomeric analogues of DMAP.

  DOI：

  10.1021/jo991011h
• 作为产物：
  描述：

  2-[4-(Boc-氨基)-3-吡啶]乙醇 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以99%的产率得到2-[4-(methylamino)-3-pyridyl]ethan-1-ol
  参考文献：
  名称：

  Configurationally Stable Biaryl Analogues of 4-(Dimethylamino)pyridine:  A Novel Class of Chiral Nucleophilic Catalysts

  摘要：

  A short synthetic approach toward a novel class of chiral nucleophilic catalysts, the dissymmetry of which stems from restricted rotation about an Ar-Ar bond, has been developed. The key steps of the synthesis include preparation of a nucleophilic 1-methyl-2-pyrrolino[3,2-c]pyridine core 16 by ortho-lithiation and creation of the biaryl axes via Suzuki cross-coupling reactions. Comparative HPLC studies of racemization for configurationally labile biaryls 31, 38, and 43 containing 1-methyl-2-pyrrolino[3,2-c]pyridine, 4-(dimethylamino)pyridine, and 4-(1-pyrrolidino)pyridine cores, respectively, have demonstrated that a pyrrolidino substituent ortho to the biaryl axis is optimal for slowing Ar-Ar rotation. Biaryls containing all three cores have been shown to retain DMAP-like catalytic activity in the acylation of a hindered alcohol. Biaryls 55 and 56, which are configurationally stable at ambient temperature, have also been prepared via modification of configurationally labile derivatives. Compounds 55 and 56 in optically pure form should provide a useful starting point for studies on catalytic asymmetric acyl transfer using atropisomeric analogues of DMAP.

  DOI：

  10.1021/jo991011h

文献信息

• Atropisomeric α-methyl substituted analogues of 4-(dimethylamino)pyridine: synthesis and evaluation as acyl transfer catalysts
  作者：Alan C. Spivey、Adrian Maddaford、David P. Leese、Alison J. Redgrave

  DOI：10.1039/b103385a

  日期：——

  The regioselectivity of α-metalation–methylation of N-BF3 adducts of 4-(dimethylamino)pyridines as a function of β-substitution is examined in attempts to prepare configurationally stable atropisomeric derivatives (I and II) having an α-methyl substituent and a β-biaryl stereogenic axis. The activity of some of these derivatives as catalysts for acyl transfer is examined and the kinetic resolution of 1-(1-naphthyl)ethanol catalysed by α-methyl chiral DMAP (−)-24 is reported. A rationale for the reduced stereoselectivity of this catalyst relative to its non-α-substituted analogue (−)-1 is also proposed.

  4-(二甲基氨基)吡啶的 N-BF3 加合物的 α-金属化-甲基化的区域选择性作为 β-取代的函数进行了检查，试图制备具有 α-甲基的构型稳定的阻转异构衍生物（I 和 II）取代基和β-联芳立体异构轴。检查了其中一些衍生物作为酰基转移催化剂的活性，并报道了 α-甲基手性 DMAP (α)-24 催化的 1-(1-萘基)乙醇的动力学拆分。还提出了该催化剂相对于其非α-取代类似物(α)-1 立体选择性降低的基本原理。