(2S)-cis-1-(tert-butyloxycarbonyl)-5-(3-pyridinyl)proline methyl ester | 229958-58-1

• 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: (2S)-cis-1-(tert-butyloxycarbonyl)-5-(3-pyridinyl)proline methyl ester
• 英文别名: 1-O-tert-butyl 2-O-methyl (2S,5R)-5-pyridin-3-ylpyrrolidine-1,2-dicarboxylate
• CAS: 229958-58-1
• 化学式: C₁₆H₂₂N₂O₄
• 分子量: 306.362
• InChiKey: FBRGAKBDPPAJQW-OLZOCXBDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  22
• 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：

  (2S)-cis-1-(tert-butyloxycarbonyl)-5-(3-pyridinyl)proline methyl ester 在 palladium on activated charcoal N-甲基咪唑 、 盐酸 、 sodium tetrahydroborate 、 正丁基锂 、 草酰氯 、 氢气 、 sodium hydride 、 二甲基亚砜 、 三乙胺 、 三氟甲烷磺酸甲酯 、 calcium chloride 、 lithium bromide 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 正己烷 、 二氯甲烷 、 乙酸乙酯 、 丙酮 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 7.5h， 生成 1-(3-pyridinyl)-8-azabicyclo<3.2.1>octane
  参考文献：
  名称：

  Conformationally Constrained Nicotines. 1-Pyridinyl-7-azabicyclo[2.2.1]heptane and 1-Pyridinyl-8-azabicyclo[3.2.1]octane Analogues

  摘要：

  Conformationally constrained bicycle analogues of natural (-)-nicotine and unnatural (+)-nicotine have been synthesized from D- and L-glutamic acid, respectively. Regioselective addition of 3-lithiopyridine to the gamma-carbonyl of a protected glutamate was followed by intramolecular imine formation and stereospecific catalytic hydrogenation of the resultant pyrroline to give cis-5-pyridinylproline. A sequence of transformations to convert the ester to bromide was followed by the key intramolecular anionic cyclization at the benzylic position to form the 1-pyridinyl-7-azabicyclo[2.2.1]heptane analogue. Alternatively, homologation of the ester of cis-5-pyridinylproline and conversion to bromide allowed cyclization to the 1-pyridinyl-7-azabicyclo[3.2.1]octane analogues.

  DOI：

  10.1021/jo990130u
• 作为产物：
  描述：

  3-碘吡啶 在 盐酸 、 acetate buffer 、 sodium cyanoborohydride 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 5.0h， 生成 (2S)-cis-1-(tert-butyloxycarbonyl)-5-(3-pyridinyl)proline methyl ester
  参考文献：
  名称：

  Conformationally Constrained Nicotines. 1-Pyridinyl-7-azabicyclo[2.2.1]heptane and 1-Pyridinyl-8-azabicyclo[3.2.1]octane Analogues

  摘要：

  Conformationally constrained bicycle analogues of natural (-)-nicotine and unnatural (+)-nicotine have been synthesized from D- and L-glutamic acid, respectively. Regioselective addition of 3-lithiopyridine to the gamma-carbonyl of a protected glutamate was followed by intramolecular imine formation and stereospecific catalytic hydrogenation of the resultant pyrroline to give cis-5-pyridinylproline. A sequence of transformations to convert the ester to bromide was followed by the key intramolecular anionic cyclization at the benzylic position to form the 1-pyridinyl-7-azabicyclo[2.2.1]heptane analogue. Alternatively, homologation of the ester of cis-5-pyridinylproline and conversion to bromide allowed cyclization to the 1-pyridinyl-7-azabicyclo[3.2.1]octane analogues.

  DOI：

  10.1021/jo990130u

文献信息

• Conformationally Constrained Nicotines. 1-Pyridinyl-7-azabicyclo[2.2.1]heptane and 1-Pyridinyl-8-azabicyclo[3.2.1]octane Analogues
  作者：Ying-zi Xu、Jaesung Choi、M. Isabel Calaza、Sean Turner、Henry Rapoport

  DOI：10.1021/jo990130u

  日期：1999.5.1

  Conformationally constrained bicycle analogues of natural (-)-nicotine and unnatural (+)-nicotine have been synthesized from D- and L-glutamic acid, respectively. Regioselective addition of 3-lithiopyridine to the gamma-carbonyl of a protected glutamate was followed by intramolecular imine formation and stereospecific catalytic hydrogenation of the resultant pyrroline to give cis-5-pyridinylproline. A sequence of transformations to convert the ester to bromide was followed by the key intramolecular anionic cyclization at the benzylic position to form the 1-pyridinyl-7-azabicyclo[2.2.1]heptane analogue. Alternatively, homologation of the ester of cis-5-pyridinylproline and conversion to bromide allowed cyclization to the 1-pyridinyl-7-azabicyclo[3.2.1]octane analogues.