N-叔-丁氧羰基新烟碱 | 154874-91-6

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 中文名称: N-叔-丁氧羰基新烟碱
• 中文别名: 1-哌啶羧酸,2-(3-吡啶基)-,1,1-二甲基乙基酯
• 英文名称: tert-butyl 2-(pyridine-3-yl)piperidine-1-carboxylate
• 英文别名: tert-butyl 2-(pyridin-3-yl)piperidine-1-carboxylate；tert-butyl-2-(pyridin-3-yl)piperidine-1-carboxylate；N-Boc-anabasine；tert-butyl 2-pyridin-3-ylpiperidine-1-carboxylate
• CAS: 154874-91-6
• 化学式: C₁₅H₂₂N₂O₂
• 分子量: 262.352
• InChiKey: QNCDRZOVLOOHOP-UHFFFAOYSA-N

物化性质

• 沸点：
  375.3±35.0 °C(Predicted)
• 密度：
  1.083±0.06 g/cm3(Predicted)
• 溶解度：
  可溶于氯仿、可溶于二氯甲烷、乙酸乙酯

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-叔-丁氧羰基新烟碱 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 以98 %的产率得到(±)-毒藜碱
  参考文献：
  名称：

  N-杂芳基卤化物的 Heck 反应用于简明合成手性 α-杂芳基取代的杂环

  摘要：

  N-杂芳基卤化物和杂环烯烃之间的 Heck 反应通过采用 P, P=O 基配体或 ( S )-DTBM-SEGPHOS 完成，导致形成各种非手性或手性 α-杂芳基取代杂环。

  DOI：

  10.1002/anie.202209087
• 作为产物：
  描述：

  N-BOC-3-氨甲基吡啶 在 四甲基乙二胺 、 仲丁基锂 作用下， 以 四氢呋喃 为溶剂， 生成 N-叔-丁氧羰基新烟碱
  参考文献：
  名称：

  Intramolecular Cyclizations of .alpha.-Lithioamine Synthetic Equivalents: Convenient Syntheses of 3-, 5-, and 6-Membered-Ring Heterocyclic Nitrogen Compounds and Elaborations of 3-Membered Ring Systems

  摘要：

  A lithiation-intramolecular cyclization reaction of N-Boc chloroalkyl secondary amines is reported to provide the 2-aryl-substituted pyrrolidine and piperidines 6, 7, 9, and 11 and a series of 2-azabicyclo[3.1.0] derivatives 14-25, including cyclopropane derivatives of proline and of the indolizidine-pyrrolizidine alkaloid ring system. Lithiation-substitutions of N-Boc-N-ethylcyclopropylamine to give 27-29 and lithiation-silylations of N-Boc aziridines to give 31-33 also are reported.

  DOI：

  10.1021/jo00081a002

文献信息

• Palladium-Catalyzed Direct C−H Arylation of <i>N</i>-Iminopyridinium Ylides:  Application to the Synthesis of (±)-Anabasine
  作者：Alexandre Larivée、James J. Mousseau、André B. Charette

  DOI：10.1021/ja710073n

  日期：2008.1.1

  Palladium-catalyzed direct C-H arylation of N-iminopyridinium ylides provides a powerful and versatile method for the synthesis of functionalized piperidines in good yields. Chemoselective functionalization of the pyridinium ring in the presence of a pyridine substituent is possible as exemplified by the expedient synthesis of anabasine in 61% overall yield over three steps.

  N-亚氨基吡啶鎓叶立德的钯催化直接 CH 芳基化为以良好的收率合成功能化哌啶提供了一种强大而通用的方法。在吡啶取代基的存在下，吡啶鎓环的化学选择性官能化是可能的，例如通过三个步骤以 61% 的总产率合成 anabasine。
• Synthesis of 2-Arylpiperidines by Palladium Couplings of Aryl Bromides with Organozinc Species Derived from Deprotonation of <i>N</i>-Boc-Piperidine
  作者：Iain Coldham、Daniele Leonori

  DOI：10.1021/ol801579r

  日期：2008.9.1

  The organolithium species derived from proton abstraction of N-Boc-piperidine with s-BuLi and TMEDA can be transmetalated to the organozinc reagent, and this organometallic species can be coupled directly with aryl bromides in a Negishi-type reaction using palladium catalysis with the ligand tri-tert-butylphosphine (t-Bu3P-HBF4). The chemistry was applied to a very short synthesis of the alkaloid anabasine

  可以将N-Boc-哌啶与s-BuLi和TMEDA的质子抽象衍生的有机锂物质进行金属转移到有机锌试剂中，并且该有机金属物质可以在Negishi型反应中与钯配体催化直接与芳基溴偶联。三叔丁基膦（t-Bu3P-HBF4）。该化学方法用于非常短的生物碱金刚烷胺的合成。
• [Co(TPP)]‐Catalyzed Formation of Substituted Piperidines
  作者：Marianne Lankelma、Astrid M. Olivares、Bas de Bruin

  DOI：10.1002/chem.201900587

  日期：2019.4.17

  the [Co(TPP)]‐catalyzed formation of useful six‐membered N‐heterocyclic piperidines directly from linear aldehydes is presented herein. The piperidines were obtained in overall high yields, with linear alkenes being formed as side products in small amounts. A DFT study was performed to gain a deeper mechanistic understanding of the cobalt(II)‐porphyrin‐catalyzed formation of pyrrolidines, piperidines

  通过钴（III）-卡宾自由基中间体进行的自由基环化是合成（杂环）环状结构的有力方法。以最近报道的Co II催化的五元N-杂环吡咯烷的合成为基础卟啉，本文介绍了直接由线性醛类[Co（TPP）]催化形成的有用的六元N-杂环哌啶。以总的高收率获得哌啶，并以少量副产物形式形成直链烯烃。进行了DFT研究，以更深入地了解钴（II）-卟啉催化的吡咯烷，哌啶和线性烯烃的形成。计算表明，烯烃不可能通过预期的1,2-氢原子转移至卡宾碳而形成。取而代之的是，该计算与涉及苄基自由基形成，随后进行自由基反弹的闭环形成哌啶的途径是一致的。竞争性1
• Application of Catalytic Dynamic Resolution of <i>N</i>-Boc-2-lithiopiperidine to the Asymmetric Synthesis of 2-Aryl and 2-Vinyl Piperidines
  作者：Timothy K. Beng、Robert E. Gawley

  DOI：10.1021/ol102682r

  日期：2011.2.4

  The highly enantioselective synthesis of 2-aryl- and 2-vinyl-piperidines has been accomplished through a catalytic dynamic resolution (CDR) of N-Boc-2-lithiopiperidine. The method has been applied to the synthesis of both enantiomers of the tobacco alkaloid anabasine.
• Expedient Synthesis of α-Heteroaryl Piperidines Using a Pd-Catalyzed Suzuki Cross-Coupling–Reduction Sequence
  作者：Kevin D. Hesp、Dilinie P. Fernando、Wenhua Jiao、Allyn T. Londregan

  DOI：10.1021/ol403367b

  日期：2014.1.17

  A method for the modular synthesis of alpha-heteroaryl piperidines is reported. The two-step procedure consists of an initial Pd-catalyzed Suzuki cross-coupling of the heteroaryl bromide with a boronate ester derived from N-Boc piperidone, followed by subsequent tetrahydropyridine reduction. Using this method, alpha-heteroaryl piperidine products featuring a broad range of pharmaceutically relevant azine and diazine substitutions have been prepared.