N-(tert-butyloxycarbonyl)-(2R,5S)-5-[3-(4'-chloropyridinyl)]proline methyl ester | 260270-24-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-(tert-butyloxycarbonyl)-(2R,5S)-5-[3-(4'-chloropyridinyl)]proline methyl ester
• 英文别名: (2R,5S)-N-(tert-butyloxycarbonyl)-5-[3-(4'-chloropyridinyl)]proline methyl ester；1-(tert-Butyl) 2-methyl (2R,5S)-5-(4-chloropyridin-3-yl)pyrrolidine-1,2-dicarboxylate；1-O-tert-butyl 2-O-methyl (2R,5S)-5-(4-chloropyridin-3-yl)pyrrolidine-1,2-dicarboxylate
• CAS: 260270-24-4
• 化学式: C₁₆H₂₁ClN₂O₄
• 分子量: 340.807
• InChiKey: PWDSNFAJNBONII-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  68.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-(tert-butyloxycarbonyl)-(2R,5S)-5-[3-(4'-chloropyridinyl)]proline methyl ester 在 吡啶 、 盐酸 、 lithium hydroxide 、 sodium hydroxide 、 正丁基锂 、 草酰氯 、 叔丁基硫醇 、 (2R,6S)-2,6-dimethylpiperidine 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 57.0h， 生成 苯乙胺,a,4-二甲基-b-苯基-
  参考文献：
  名称：

  Enantiospecific Synthesis of Annulated Nicotine Analogues from d-Glutamic Acid. 7-Azabicyclo[2.2.1]heptano[2.3-c]pyridines

  摘要：

  The conformationally restricted nicotinoid (1S,4S)-7-methyl-7-azabicyclo[2.2.1]heptano[2,3-c]pyridine dihydrochloride has been prepared enantiospecifically from D-glutamic acid, The method involved a lithium cis-2,6-dimethylpiperidide-mediated intramolecular anionic cyclization of (2S,5R)-N-(tert-butyloxycarbonyl)-5-[3-(4-N-chloropyridinyl]proline methyl ester in tandem with a standard decarboxylation sequence. Reductive amination afforded the desired N-methylated [2.2.1]bicyclonicotinoid. Cyclization of the corresponding iodopyridinylproline methyl ester, obtained via ultrasound-facilitated chloro-iodo exchange, was also effected.

  DOI：

  10.1021/jo010534y
• 作为产物：
  描述：

  二碳酸二叔丁酯 、 (2R)-5-[3-(4'-chloropyridinyl)]proline methyl ester 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以6.45 g的产率得到N-(tert-butyloxycarbonyl)-(2R,5S)-5-[3-(4'-chloropyridinyl)]proline methyl ester
  参考文献：
  名称：

  Enantiospecific Synthesis of Annulated Nicotine Analogues from d-Glutamic Acid. 7-Azabicyclo[2.2.1]heptano[2.3-c]pyridines

  摘要：

  The conformationally restricted nicotinoid (1S,4S)-7-methyl-7-azabicyclo[2.2.1]heptano[2,3-c]pyridine dihydrochloride has been prepared enantiospecifically from D-glutamic acid, The method involved a lithium cis-2,6-dimethylpiperidide-mediated intramolecular anionic cyclization of (2S,5R)-N-(tert-butyloxycarbonyl)-5-[3-(4-N-chloropyridinyl]proline methyl ester in tandem with a standard decarboxylation sequence. Reductive amination afforded the desired N-methylated [2.2.1]bicyclonicotinoid. Cyclization of the corresponding iodopyridinylproline methyl ester, obtained via ultrasound-facilitated chloro-iodo exchange, was also effected.

  DOI：

  10.1021/jo010534y

文献信息

• Enantiospecific Synthesis of Annulated Nicotine Analogues from <scp>d</scp>- and <scp>l</scp>-Glutamic Acid. Pyridotropanes
  作者：Sean C. Turner、Hongbin Zhai、Henry Rapoport

  DOI：10.1021/jo991609p

  日期：2000.2.1

  The conformationally restricted nicotinoid 1-methyl-8-azabicyclo[3.2.1]octano[2,3-c]pyridine, pyrido[3,4-b]tropane, has been prepared enantiospecifically from both d- and l-glutamic acid. The method involved coupling of pyroglutamic acid derivatives with ortho-lithiated 4-chloropyridine, followed by intramolecular imine formation and reduction to generate the d- and l-5-substituted proline esters.

  构象受限的类烟碱 1-methyl-8-azabicyclo[3.2.1]octano[2,3-c]pyridine, pyrido[3,4-b]tropane 是由 d- 和 l- 谷氨酸制备的。该方法涉及将焦谷氨酸衍生物与邻位锂化的 4-氯吡啶偶联，然后形成分子内亚胺并还原生成 d-和 l-5-取代的脯氨酸酯。氯碘交换和侧链延伸为 [3.2.1] 系统提供了前体。8-氮杂双环[3.2.1]辛基-[2,3-c]吡啶骨架的构建是通过分子内Heck反应实现的。随后的臭氧分解产生的酮被还原为甲醇或亚甲基，产生融合的尼古丁类似物。
• Enantiospecific Synthesis of Annulated Nicotine Analogues from <scp>d</scp>-Glutamic Acid. 7-Azabicyclo[2.2.1]heptano[2.3-<i>c</i>]pyridines
  作者：Joseph R. Lennox、Sean C. Turner、Henry Rapoport

  DOI：10.1021/jo010534y

  日期：2001.10.1

  The conformationally restricted nicotinoid (1S,4S)-7-methyl-7-azabicyclo[2.2.1]heptano[2,3-c]pyridine dihydrochloride has been prepared enantiospecifically from D-glutamic acid, The method involved a lithium cis-2,6-dimethylpiperidide-mediated intramolecular anionic cyclization of (2S,5R)-N-(tert-butyloxycarbonyl)-5-[3-(4-N-chloropyridinyl]proline methyl ester in tandem with a standard decarboxylation sequence. Reductive amination afforded the desired N-methylated [2.2.1]bicyclonicotinoid. Cyclization of the corresponding iodopyridinylproline methyl ester, obtained via ultrasound-facilitated chloro-iodo exchange, was also effected.