(8S,9S)-6'-methoxy-9-phenyl-cinchonan | 1007362-77-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: (8S,9S)-6'-methoxy-9-phenyl-cinchonan
• 英文别名: (9S)-9-phenyl-9-deoxy-quinine；(9S)-9-phenylquinine；9-phenyl-9-deoxy quinine；(8I+/-,9S)-6a(2)-Methoxy-9-phenylcinchonan；4-[(S)-[(2S,4S,5R)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl]-phenylmethyl]-6-methoxyquinoline
• CAS: 1007362-77-7
• 化学式: C₂₆H₂₈N₂O
• 分子量: 384.521
• InChiKey: BNAZJSZFIPXMAN-QRRBZYCPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  25.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (8S,9S)-6'-methoxy-9-phenyl-cinchonan 在 sodium hydride 、 水 作用下， 以 二甲基亚砜 、 mineral oil 为溶剂， 反应 0.42h， 生成 9R-phenyl-9-deoxyquinine
  参考文献：
  名称：

  通过比较实验数据和从头算算得出的NMR数据差异，将构型分配给非对映四联体的置换方法。

  摘要：

  四个非对映体组的实验化学位移偏差和DFT / GIAO计算的各向同性屏蔽的偏差的评分排列可以帮助分配其相对构型。在一组非对映体金鸡纳生物碱衍生物上应用了该方法，其中13 C NMR数据始终可确定适当的构型。提出的方法也是尝试通过排除来量化分配。

  DOI：

  10.3762/bjoc.13.245
• 作为产物：
  描述：

  溴苯 、 (8alpha,9R)-9-氯-6'-甲氧基脱氧辛可宁 在 magnesium 、 1,2-二溴乙烷 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 4.0h， 以70%的产率得到(8S,9S)-6'-methoxy-9-phenyl-cinchonan
  参考文献：
  名称：

  Stereoselective C9 Arylation and Vinylation of Cinchona Alkaloids

  摘要：

  A simple and efficient method for the highly stereoselective C-9 arylation and vinylation of Cinchona alkaloids was developed. Both 9s- and 9R-chloroquinine with PhMgBr yielded 9S-phenylquinine (X-ray structure). The reactions with various aryl and vinyl Grignard reagents resulted in the series of 9S-aryl and vinyl alkaloid derivatives. The stereochemical outcome was rationalized by coordination of the magnesium atom to the quinuclidine nitrogen, thus directing the nucleophilic attack at the C-9 stereogenic center.

  DOI：

  10.1021/ol7026625

文献信息

• Highly tunable arylated cinchona alkaloids as bifunctional catalysts
  作者：Cormac Quigley、Zaida Rodríguez-Docampo、Stephen J. Connon

  DOI：10.1039/c1cc14684j

  日期：——

  We report the design and evaluation of a library of chiral bifunctional organocatalysts in which the distance between the catalytically active units can be systematically varied.

  我们报道了一种手性双功能有机催化剂库的设计与评估，其中催化活性单元之间的距离可以系统地变化。
• New Functional Derivatives of 9-Phenylquinine
  作者：Jacek Skarżewski、Przemysaw Boratyński

  DOI：10.1055/s-0029-1216933

  日期：2009.9

  A rapid synthesis of various 9-aryl derivatives of quinine is presented. They are obtained via coupling reactions of functionalized arylmagnesium halides and 9-chloroquinine.

  本文介绍了奎宁的各种 9-芳基衍生物的快速合成方法。它们是通过官能化芳基卤化镁和 9-氯奎宁的偶联反应获得的。
• Synthetic approaches to 9-arylated Cinchona alkaloids: stereoselective addition of Grignard reagents to cinchonanones and hydroxylation of 9-phenylcinchonanes
  作者：Przemysław J. Boratyński、Ilona Turowska-Tyrk、Jacek Skarżewski

  DOI：10.1016/j.tetasy.2012.05.024

  日期：2012.6

  All 8,9-isomers of the 9-phenyl Cinchona alkaloids were obtained by autoxidation of 9-deoxy-9-phenyl-alkaloids and by the addition of Grignard reagents to the respective ketones. The diastereoselective addition of phenyl-, methyl-, and vinylmagnesium reagents to quinidinone and cinchoninone gave the corresponding (8R,9S)-products with acceptable yields and starting material recovery. The configurations of the compounds obtained were established by chemical correlations, NMR experiments, and were supported by DFT calculations and X-ray structures. Stereochemical models for both reactions were also devised and discussed. (c) 2012 Elsevier Ltd. All rights reserved.
• Stereoselective C9 Arylation and Vinylation of <i>Cinchona</i> Alkaloids
  作者：Przemysław J. Boratyński、Ilona Turowska-Tyrk、Jacek Skarżewski

  DOI：10.1021/ol7026625

  日期：2008.2.1

  A simple and efficient method for the highly stereoselective C-9 arylation and vinylation of Cinchona alkaloids was developed. Both 9s- and 9R-chloroquinine with PhMgBr yielded 9S-phenylquinine (X-ray structure). The reactions with various aryl and vinyl Grignard reagents resulted in the series of 9S-aryl and vinyl alkaloid derivatives. The stereochemical outcome was rationalized by coordination of the magnesium atom to the quinuclidine nitrogen, thus directing the nucleophilic attack at the C-9 stereogenic center.
• A permutation approach to the assignment of the configuration to diastereomeric tetrads by comparison of experimental and ab initio calculated differences in NMR data
  作者：Przemysław J Boratyński

  DOI：10.3762/bjoc.13.245

  日期：——

  help to assign their relative configurations. This method was exercised on a set of diastereomeric Cinchona alkaloid derivatives, where 13C NMR data always identified the proper configuration. The presented approach is also an attempt to quantify the assignment by exclusion.

  四个非对映体组的实验化学位移偏差和DFT / GIAO计算的各向同性屏蔽的偏差的评分排列可以帮助分配其相对构型。在一组非对映体金鸡纳生物碱衍生物上应用了该方法，其中13 C NMR数据始终可确定适当的构型。提出的方法也是尝试通过排除来量化分配。