7-bromo-1-methyl-2-pyrrolino[3,2-c]pyridine | 219834-82-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯并吡啶类
• 英文名称: 7-bromo-1-methyl-2-pyrrolino[3,2-c]pyridine
• 英文别名: 7-bromo-1-methyl-1H,2H,3H-pyrrolo[3,2-c]pyridine；7-bromo-1-methyl-2,3-dihydropyrrolo[3,2-c]pyridine
• CAS: 219834-82-9
• 化学式: C₈H₉BrN₂
• 分子量: 213.077
• InChiKey: MJIZGJJFNGFCIF-UHFFFAOYSA-N

物化性质

• 沸点：
  294.3±40.0 °C(Predicted)
• 密度：
  1.533±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  16.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  7-bromo-1-methyl-2-pyrrolino[3,2-c]pyridine 在 palladium on activated charcoal 吡啶 、 四(三苯基膦)钯 、 氢气 、 sodium carbonate 作用下， 以 乙二醇二甲醚 、 乙醇 、 水 、 甲苯 为溶剂， 反应 52.0h， 生成 (+/-)-1-methyl-7-(2-phenylnaphthyl)-2-pyrrolino[3,2-c]pyridine
  参考文献：
  名称：

  Synthesis of atropisomeric analogues of DMAP

  摘要：

  A method for the preparation of 7-aryl derivatives of N-methyl-5-azaindoline involving Suzuki cross-coupling is described. Certain biaryls prepared in this manner exhibit atropisomerism. in particular, azaindoline 11 is shown to be configurationally stable at room temperature and to catalyse efficiently the esterification of 1-methylcyclohexanol with Ac2O. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01951-0
• 作为产物：
  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

文献信息

• Single-Handed Helical Poly(quinoxaline-2,3-diyl)s Bearing Achiral 4-Aminopyrid-3-yl Pendants as Highly Enantioselective, Reusable Chiral Nucleophilic Organocatalysts in the Steglich Reaction
  作者：Takeshi Yamamoto、Ryo Murakami、Michinori Suginome

  DOI：10.1021/jacs.6b12349

  日期：2017.2.22

  Helically chiral poly(quinoxaline-2,3-diyl)s bearing 4-aminopyrid-3-yl pendants were synthesized as new helical-polymer-based chiral nucleophilic organocatalysts. The obtained chiral nucleophilic polymer catalysts exhibited high catalytic activity, enantioselectivity, and reusability in asymmetric Steglich rearrangement of oxazolyl carbonate to C-carboxyazlactone. The polyquinoxaline-based, helically

  带有 4-aminopyrid-3-yl 侧链的螺旋手性聚 (quinoxaline-2,3-diyl)s 被合成为新的基于螺旋聚合物的手性亲核有机催化剂。获得的手性亲核聚合物催化剂在恶唑基碳酸酯不对称 Steglich 重排为 C-羧基唑内酯中表现出高催化活性、对映选择性和可重复使用性。与已知的基于小分子的手性有机催化剂相比，基于聚喹喔啉的螺旋手性 DMAP 催化剂选择性介导分子内酰基转移，后者也介导分子间酰基转移。
• Synthesis of atropisomeric analogues of DMAP
  作者：Alan C. Spivey、Tomasz Fekner、Harry Adams

  DOI：10.1016/s0040-4039(98)01951-0

  日期：1998.11

  A method for the preparation of 7-aryl derivatives of N-methyl-5-azaindoline involving Suzuki cross-coupling is described. Certain biaryls prepared in this manner exhibit atropisomerism. in particular, azaindoline 11 is shown to be configurationally stable at room temperature and to catalyse efficiently the esterification of 1-methylcyclohexanol with Ac2O. (C) 1998 Elsevier Science Ltd. All rights reserved.
• US7291739B2
  申请人：——

  公开号：US7291739B2

  公开（公告）日：2007-11-06
• Configurationally Stable Biaryl Analogues of 4-(Dimethylamino)pyridine:  A Novel Class of Chiral Nucleophilic Catalysts
  作者：Alan C. Spivey、Tomasz Fekner、Sharon E. Spey、Harry Adams

  DOI：10.1021/jo991011h

  日期：1999.12.1

  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.