(S)-2-[(E)-苯乙烯基]哌啶-1-羧酸叔丁酯 | 220926-89-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 中文名称: (S)-2-[(E)-苯乙烯基]哌啶-1-羧酸叔丁酯
• 英文名称: (S)-2-[(E)-styryl]piperidine-1-carboxylic acid tert-butyl ester
• 英文别名: (S)-N-(tert-butoxycarbonyl)-2-(trans-β-styryl)piperidine；(2S)-2-(E)-styrylpiperidine-1-carboxylic acid tert-butyl ester；tert-butyl (2S)-2-[(E)-2-phenylethenyl]piperidine-1-carboxylate
• CAS: 220926-89-6
• 化学式: C₁₈H₂₅NO₂
• 分子量: 287.402
• InChiKey: VQLPMQJOAZCUPM-DBTPVHCXSA-N

物化性质

• 熔点：
  60-62 °C
• 沸点：
  392.2±31.0 °C(Predicted)
• 密度：
  1.093±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-2-[(E)-苯乙烯基]哌啶-1-羧酸叔丁酯 在 ruthenium trichloride 、 sodium periodate 作用下， 以 四氯化碳 、 水 、 乙腈 为溶剂， 反应 5.0h， 生成 N-Boc-L-哌啶-2-羧酸
  参考文献：
  名称：

  Asymmetric Syntheses of N-Boc 2-Substituted Pyrrolidines and Piperidines by Intramolecular Cyclization

  摘要：

  Asymmetric lithiation-substitutions by n-BuLi/(-)-sparteine with the N-Boc-N-(3-halopropyl)allylamines 1-4 provide the N-Boc-2-alkenylpyrrolidines (S)-5, (S)-6, and (S)-7 in yields of 31-93% with enantiomeric ratios (ers) from 65:35 to 90:10. These reactions are shown to involve an initial asymmetric deprotonation, but the enantiodetermining step is a subsequent asymmetric cyclization under the influence of the chiral ligand. Extension to formation of a piperidine is illustrated by reaction of N-Boc-(4-chlorobutyl)cinnamylamine (9) to afford (S)-N-Boc-2-(trans-beta-styryl)piperidine ((S)-10) in 68% yield with an enantiomeric ratio (er) of 84:16. Analogous reactions with epoxide ring openings of N-Boc-N-(oxaalkenyl)benzylamines 11 and 12 afford the corresponding N-Boc-2-phenyl-3-(hydroxymethyl)pyrrolidine (13) in 67% yield with a diastereomeric ratio (dr) of 50:50 and ers of 97:3 and 95:5 and the corresponding N-Boc-2-phenyl-3-(hydroxymethyl)piperidine (14) in 29% yield with a dr of 86:14 and ers of 81:19 and 86:14.

  DOI：

  10.1021/jo981553j
• 作为产物：
  描述：

  1-Boc-哌啶 在 四丁基溴化铵 、 仲丁基锂 、 palladium diacetate 、 三乙胺 、 1,3-二-叔丁基咪唑氯化物 、 (+)-鹰爪豆碱 作用下， 以 乙醚 、 乙醇 、 水 为溶剂， 反应 11.0h， 生成 (S)-2-[(E)-苯乙烯基]哌啶-1-羧酸叔丁酯
  参考文献：
  名称：

  Pd- N -heterocyclic carbene catalyzed synthesis of piperidine alkene–alkaloids and their anti-cancer evaluation

  摘要：

  A facile synthesis of piperidine alkene-alkaloids including natural (+)-Caulophyllumine B in high yields has been developed by Heck cross-coupling reaction catalyzed by simple in situ formed palladium-N-heterocyclic carbenes (Pd-NHCs). Formation of Pd(0) nanoparticles has been noticed during the reaction course. The synthesized piperidine alkene-alkaloids were evaluated for in vitro anti-cancer activity against a panel of human tumor cell lines of lung, breast and ovarian. Several of these piperidine alkene-alkaloids were found to possess highest growth inhibition activity than the standard drug cisplatin and support the concept to modulate drug receptor interaction. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2013.12.108

文献信息

• Preparation of Enantiopure Substituted Piperidines Containing 2-Alkene or 2-Alkyne Chains: Application to Total Syntheses of Natural Quinolizidine-Alkaloids
  作者：Guolin Cheng、Xinyan Wang、Deyong Su、Hui Liu、Fei Liu、Yuefei Hu

  DOI：10.1021/jo902615u

  日期：2010.3.19

  nonracemic Betti base as a chiral auxiliary. The key step is that the auxiliary residue was removed by a novel base-catalyzed N-debenzylation via a formation of o-quinone methide mechanism in stead of the traditional hydrogenolysis, by which the alkene or alkyne groups survived. By this method, ten 2-alkene- or 2-alkyne-containing chain substituted piperidines were prepared on the gram scale within

  通过使用非外消旋的Betti碱作为手性助剂，建立了制备对映体纯的含2个烯烃或2个炔烃的链取代哌啶的一般方法。关键步骤是代替传统的氢解反应，通过传统的氢解反应，通过邻甲基苯甲酸甲酯的形成，通过新颖的碱催化的N-脱苄基反应去除了辅助残基。通过这种方法，在数小时内以克为单位制备了十个含2-烯烃或2-炔烃的链取代的哌啶。为了证明该方法的有效性和产品的多功能性，使用（S）-2-烯丙基完成了天然生物碱（+）-peltierine，（-）-lasubine II和（+）-cermizine C的总合成--N -Boc-哌啶为通用成分。
• Asymmetric Syntheses of N-Boc 2-Substituted Pyrrolidines and Piperidines by Intramolecular Cyclization
  作者：Caterina Serino、Nathan Stehle、Yong Sun Park、Saverio Florio、Peter Beak

  DOI：10.1021/jo981553j

  日期：1999.2.1

  Asymmetric lithiation-substitutions by n-BuLi/(-)-sparteine with the N-Boc-N-(3-halopropyl)allylamines 1-4 provide the N-Boc-2-alkenylpyrrolidines (S)-5, (S)-6, and (S)-7 in yields of 31-93% with enantiomeric ratios (ers) from 65:35 to 90:10. These reactions are shown to involve an initial asymmetric deprotonation, but the enantiodetermining step is a subsequent asymmetric cyclization under the influence of the chiral ligand. Extension to formation of a piperidine is illustrated by reaction of N-Boc-(4-chlorobutyl)cinnamylamine (9) to afford (S)-N-Boc-2-(trans-beta-styryl)piperidine ((S)-10) in 68% yield with an enantiomeric ratio (er) of 84:16. Analogous reactions with epoxide ring openings of N-Boc-N-(oxaalkenyl)benzylamines 11 and 12 afford the corresponding N-Boc-2-phenyl-3-(hydroxymethyl)pyrrolidine (13) in 67% yield with a diastereomeric ratio (dr) of 50:50 and ers of 97:3 and 95:5 and the corresponding N-Boc-2-phenyl-3-(hydroxymethyl)piperidine (14) in 29% yield with a dr of 86:14 and ers of 81:19 and 86:14.
• Pd- N -heterocyclic carbene catalyzed synthesis of piperidine alkene–alkaloids and their anti-cancer evaluation
  作者：Shravankumar Kankala、Ranjith Kumar Kankala、Ramesh Balaboina、Narasimha Swamy Thirukovela、Ravinder Vadde、Chandra Sekhar Vasam

  DOI：10.1016/j.bmcl.2013.12.108

  日期：2014.2

  A facile synthesis of piperidine alkene-alkaloids including natural (+)-Caulophyllumine B in high yields has been developed by Heck cross-coupling reaction catalyzed by simple in situ formed palladium-N-heterocyclic carbenes (Pd-NHCs). Formation of Pd(0) nanoparticles has been noticed during the reaction course. The synthesized piperidine alkene-alkaloids were evaluated for in vitro anti-cancer activity against a panel of human tumor cell lines of lung, breast and ovarian. Several of these piperidine alkene-alkaloids were found to possess highest growth inhibition activity than the standard drug cisplatin and support the concept to modulate drug receptor interaction. (C) 2013 Elsevier Ltd. All rights reserved.