trans-3-bromo-2-methoxy-1-(methoxycarbonyl)piperidine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: trans-3-bromo-2-methoxy-1-(methoxycarbonyl)piperidine
• 英文别名: methyl (2R,3S)-3-bromo-2-methoxypiperidine-1-carboxylate
• 化学式: C₈H₁₄BrNO₃
• 分子量: 252.108
• InChiKey: YSZAMLRAOVWDMX-NKWVEPMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  trans-3-bromo-2-methoxy-1-(methoxycarbonyl)piperidine 在 四氯化钛 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.5h， 生成 2-cyano-1,4,5,6-tetrahydro-1-pyridinecarboxylic acid methyl ester
  参考文献：
  名称：

  Reactivity of 2-cyano-1,4,5,6-tetrahydro-1-pyridinecarboxylic acid esters towards various nucleophiles: Regio- and stereoselectivity of the attack

  摘要：

  The synthesis and reactivity of the title compounds towards nucleophiles are discussed. The regio-and diastereoselectivity of the attack is highly dependent on the carbamic ester and the type of nucleophile applied. Both Michael type addition across the activated double bond and S(N)2T reaction at the carbamate carbon atom were observed. Structure assignment of the adducts in solution and in the solid state was performed utilizing high temperature NMR techniques as well as single crystal X-ray diffraction.

  DOI：

  10.1007/bf00806971
• 作为产物：
  描述：

  甲基3,6-二氢-2H-吡啶-1-羧酸酯 在 palladium on activated charcoal 溴 作用下， 以 四氢呋喃 、 甲醇 、 三乙胺 为溶剂， 反应 48.0h， 生成 trans-3-bromo-2-methoxy-1-(methoxycarbonyl)piperidine
  参考文献：
  名称：

  Reactivity of 2-cyano-1,4,5,6-tetrahydro-1-pyridinecarboxylic acid esters towards various nucleophiles: Regio- and stereoselectivity of the attack

  摘要：

  The synthesis and reactivity of the title compounds towards nucleophiles are discussed. The regio-and diastereoselectivity of the attack is highly dependent on the carbamic ester and the type of nucleophile applied. Both Michael type addition across the activated double bond and S(N)2T reaction at the carbamate carbon atom were observed. Structure assignment of the adducts in solution and in the solid state was performed utilizing high temperature NMR techniques as well as single crystal X-ray diffraction.

  DOI：

  10.1007/bf00806971

文献信息

• A New and Efficient Synthesis of Derivatives of Octahydro-4H-pyrrolo[1,2-c]pyrido[1′,2′-a]imidazole
  作者：Anne Rouchaud、Jean-Claude Braekman

  DOI：10.1002/ejoc.201001704

  日期：2011.4

  developed. The elaborated pathway was adapted to access derivatives related to 6 that differed in their C-4 substituent. A new and efficient synthesis of derivatives of the tricyclic heterocycle A from lysine is described. A mechanism involving 3-halopiperideines as intermediates and based on a ring contraction followed by Michael reaction is proposed and tested. Copyright © 2011 WILEY-VCH Verlag GmbH

  当将丙二酸二乙酯加入 Δ 1-哌啶的溶液中时，由 N-溴代琥珀酰亚胺 (NBS) 氧化脱氨和脱羧 L-赖氨酸原位生成，形成意想不到的三环化合物 6 (4-二乙基丙二酰-八氢-4H-观察到吡咯并[1,2-c]吡啶并[1', 2'-a]咪唑)。6 的结构是从其光谱数据的分析中推导出来的，并通过化学降解和全合成得到证实。我们证明 3-bromo-1-piperideine 与它的形成有关。此外，基于此特性，开发了一种新的高效合成 6。精心设计的途径适用于访问与 6 相关的衍生物，这些衍生物的 C-4 取代基不同。描述了一种从赖氨酸合成三环杂环 A 衍生物的新的有效方法。提出并测试了一种涉及 3-卤代哌啶作为中间体并基于环收缩和迈克尔反应的机制。版权所有 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim。