α-allyl-N-benzyloxycarbonylpiperidine | 493009-89-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: α-allyl-N-benzyloxycarbonylpiperidine
• 英文别名: benzyl 2-allylpiperidine-1-carboxylate；Benzyl 2-(prop-2-en-1-yl)piperidine-1-carboxylate；benzyl 2-prop-2-enylpiperidine-1-carboxylate
• CAS: 493009-89-5
• 化学式: C₁₆H₂₁NO₂
• 分子量: 259.348
• InChiKey: DZLUMARNZBXDOK-UHFFFAOYSA-N

物化性质

• 沸点：
  368.6±21.0 °C(Predicted)
• 密度：
  1.058±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 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：

  α-allyl-N-benzyloxycarbonylpiperidine 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 反应 8.0h， 生成 2-丙基哌啶
  参考文献：
  名称：

  High regioselectivity in electrochemical α-methoxylation of N-protected cyclic amines

  摘要：

  N-Protecting groups of alpha-substituted cyclic amines strongly affected the regioselectivity in electrochemical methoxylation of these compounds. Namely, N-acyl derivatives were transformed into alpha'-methoxylated compounds, while N-cyano derivatives changed into alpha-methoxylated derivatives. Furthermore, Lewis acid catalyzed nucleophilic substitution of the alpha-methoxylated compounds protected with cyano group afforded alpha,alpha-disubstituted cyclic amines. (c) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.02.060
• 作为产物：
  描述：

  (Z)-octa-5,7-dien-1-amine 在 silver tetrafluoroborate 、 2,6-双(二苯基膦甲基)吡啶二氯化钯 、 magnesium sulfate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 18.17h， 生成 α-allyl-N-benzyloxycarbonylpiperidine
  参考文献：
  名称：

  钯（II）催化的1,3-二烯的分子内加氢胺化反应得到均烯丙基胺

  摘要：

  高选择性的选择：受保护的1，3-二烯氨基的轻度钯催化加氢胺化是可能的。这种高度区域选择性的反应使用三齿PNP钳形配体，并以高收率得到环状和均烯丙基保护的胺。具有多种胺保护基和二烯取代模式的底物被环化以形成五元和六元杂环。PG ＝保护基。

  DOI：

  10.1002/anie.201305766

文献信息

• Electrochemical Deallylation of α-Allyl Cyclic Amines and Synthesis of Optically Active Quaternary Cyclic Amino Acids
  作者：Peter G. Kirira、Masami Kuriyama、Osamu Onomura

  DOI：10.1002/chem.200903512

  日期：2010.4.6

  Electrochemical oxidation of α‐allylated and α‐benzylated N‐acylated cyclic amines by using a graphite anode easily affords the corresponding α‐methoxylated products with up to 76 % yield. Ease of oxidation was affected by the type of electrode, the size of cyclic amine, and the nature of the protecting group. This method was successfully applied to the synthesis of optically active N‐acylated α‐alkyl‐α‐amino

  通过使用石墨阳极对α-烯丙基化和α-苄基化N-酰化的环状胺进行电化学氧化，可以轻松获得相应的α-甲氧基化产物，收率高达76％。电极的类型，环胺的大小和保护基的性质会影响氧化的难易程度。该方法已成功应用于合成具有高达99％ee的旋光性N酰化的α-烷基-α-氨基酸酯 。
• Solid-Phase Synthesis of Piperidines by N-Acyliminium Ion Chemistry
  作者：Johan J. N. Veerman、Jasper Klein、René W. M. Aben、Hans W. Scheeren、Chris G. Kruse、Jan H. van Maarseveen、Floris P. J. T. Rutjes、Henk Hiemstra

  DOI：10.1002/1099-0690(200209)2002:18<3133::aid-ejoc3133>3.0.co;2-h

  日期：2002.9

  An efficient solid-phase procedure for the synthesis of a number of 2-substituted piperidines is reported. Starting from solid-supported carbamate-tethered delta-amino acetals, 2-benzotriazolyl-substituted (Bt-substituted) piperidines were obtained by acid-induced ring-closure followed by trapping of the transient N-acyliminium ions with benzotriazole. These 2-Bt-substituted piperidines were then used as precursors for the successful introduction of several C-nucleophiles by N-acyliminium. ion chemistry. (C) Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
• High regioselectivity in electrochemical α-methoxylation of N-protected cyclic amines
  作者：Samuel S. Libendi、Yosuke Demizu、Yoshihiro Matsumura、Osamu Onomura

  DOI：10.1016/j.tet.2008.02.060

  日期：2008.4

  N-Protecting groups of alpha-substituted cyclic amines strongly affected the regioselectivity in electrochemical methoxylation of these compounds. Namely, N-acyl derivatives were transformed into alpha'-methoxylated compounds, while N-cyano derivatives changed into alpha-methoxylated derivatives. Furthermore, Lewis acid catalyzed nucleophilic substitution of the alpha-methoxylated compounds protected with cyano group afforded alpha,alpha-disubstituted cyclic amines. (c) 2008 Elsevier Ltd. All rights reserved.
• Palladium(II)-Catalyzed Intramolecular Hydroamination of 1,3-Dienes to Give Homoallylic Amines
  作者：Justin M. Pierson、Erica L. Ingalls、Richard D. Vo、Forrest E. Michael

  DOI：10.1002/anie.201305766

  日期：2013.12.9

  A pincer for high selectivity: A mild palladium‐catalyzed hydroamination of protected amino‐1,3‐dienes is possible. This highly regioselective reaction employs a tridentate PNP pincer ligand and leads to cyclic and homoallylic protected amines in high yields. Substrates with a wide array of amine protecting groups and diene substitution patterns were cyclized to form five‐ and six‐membered heterocycles

  高选择性的选择：受保护的1，3-二烯氨基的轻度钯催化加氢胺化是可能的。这种高度区域选择性的反应使用三齿PNP钳形配体，并以高收率得到环状和均烯丙基保护的胺。具有多种胺保护基和二烯取代模式的底物被环化以形成五元和六元杂环。PG ＝保护基。