3-bromo-cis-2,6-diallyl-1,2,5,6-tetrahydropyridine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 3-bromo-cis-2,6-diallyl-1,2,5,6-tetrahydropyridine
• 英文别名: cis-3-bromo-2,6-diallyl-1,2,5,6-tetrahydropyridine；cis-2,6-diallyl-3-bromo-1,2,5,6-tetrahydropyridine；(2R,6S)-5-bromo-2,6-bis(prop-2-enyl)-1,2,3,6-tetrahydropyridine
• 化学式: C₁₁H₁₆BrN
• 分子量: 242.159
• InChiKey: LGNKGKDUJMBEBL-KOLCDFICSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-bromo-cis-2,6-diallyl-1,2,5,6-tetrahydropyridine 在 Grubbs catalyst first generation 盐酸 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 6.17h， 生成 7-bromo-10-azabicyclo[4.3.1]deca-3,7-diene hydrochloride
  参考文献：
  名称：

  通过二烯丙基硼化-闭环复分解序列从吡啶和吡咯合成桥连氮杂双环

  摘要：

  详细阐述了通过二烯丙基硼化-闭环复分解（RCM）序列制备桥连氮杂双环的简单方法。复分解反应的前体是通过芳香杂环如吡啶、异喹啉和吡咯与三烯丙基硼烷和醇的还原转二烯丙基化反应制备的。用一当量的三烯丙基硼烷加热反式异构体，可以得到相应的顺式异构体——或（在吡咯的情况下）顺式和反式异构体的混合物。胺官能团的 Boc 保护提供了具有烯丙基轴向取向的 RCM 反应的前体。该阶段的化学产率非常好，反应所需的格鲁布斯催化剂量不超过2.5 mol-%（第一代催化剂）或3.7 mol-%（第二代催化剂）。氮杂双环[4.2. 1]壬烯，从吡咯获得，是毒蕈胺的关键结构基序。通过单晶X射线分析研究了cis-1,3-diallyl-1,2,3,4-四氢异喹啉和氮杂双环[4.3.1]癸二烯的结构。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

  DOI：

  10.1002/ejoc.200500560
• 作为产物：
  描述：

  3-bromo-trans-2,6-diallyl-1,2,5,6-tetrahydropyridine 在 三烯丙基硼烷 、 sodium hydroxide 作用下， 生成 3-bromo-cis-2,6-diallyl-1,2,5,6-tetrahydropyridine
  参考文献：
  名称：

  Reductivetrans-2,6-diallylation of pyridines with allylboranes. Synthesis oftrans- andcis-2,6-diallyl-1,2,5,6-tetrahydropyridines and their deuterated derivatives

  摘要：

  The reductive trans-2,6-diallylation of pyridines with triallyl- and allyI(dialkyl)boranes has been discovered. Heating (40-100 degrees C) of pyridine, deuteropyridine, or 3-bromopyridine complexes with triallylborane in the presence of alcohols (ROH or CH3OD), water, or Et(2)NH results in the respective trans-2,6-diallyl-1,2,5,6-tetrahydropyridines (2, 3, 22, or 25) In 20-97% yields. A preparative method for the isomerization of trans-2,6-diallyl compounds 2 and 25 into the respective cis-isomers 4 and 28 by heating them with triallyl- or allyl(dialkyl)boranes (125-150 degrees C) has been suggested. The hydrogenation of trans- or cis-2,6-diallyl-1,2,5,6-tetrahydropyridines gave trans- or cis-2,6-dipropylpiperidines, respectively. The cis- and trans-configurations of compounds 2 and 4 were established by analyzing the NMR spectra of N-benzyl (7 and 13) and N,N-dimethyl (6 and 14) derivatives of piperidine derivatives 5 and 8. A possible mechanism for the reductive diallylation of pyridines has been discussed.

  DOI：

  10.1007/bf00699842

文献信息

• Synthesis and molecular structure of 3-bromo-trans-2,6-diallyl-?3-piperideine hydrochloride
  作者：Yu. N. Bubnov、E. A. Shagova、S. V. Evchenko、M. O. Dekaprilevich、Yu. T. Struchkov

  DOI：10.1007/bf00699843

  日期：1994.4

  The structure of 3-bromo-trans-2,6-diallyl-Delta(3)-piperideine hydrochloride was determined by X-ray diffraction analysis. The corresponding base was prepared by reductive diallylation of 3-bromopyridine with triallylborane. 3-Bromo-cis-2,6-diallyl-Delta(3)-piperideine 3 was prepared by heating trans-isomer 2 with traillylborane at 130 degrees C followed by deboronation of the resulting aminoborane with a solution of sodium hydroxide.
• Thermaltrans-cis-isomerization oftrans-2,6-diallyl-?3-piperideiiie by the action of triallylborane
  作者：Yu. N. Bubnov、E. A. Shagova、S. V. Evchenko、A. V. Ignatenko

  DOI：10.1007/bf00699209

  日期：1993.9