trans-2-allyl-6-methyl-1,2,3,6-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: trans-2-allyl-6-methyl-1,2,3,6-tetrahydropyridine
• 英文别名: (2R,6R)-2-Allyl-6-methyl-1,2,3,6-tetrahydropyridine；(2R,6R)-6-methyl-2-prop-2-enyl-1,2,3,6-tetrahydropyridine
• 化学式: C₉H₁₅N
• 分子量: 137.225
• InChiKey: PSNCFOFVFFJWLI-RKDXNWHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  trans-2-allyl-6-methyl-1,2,3,6-tetrahydropyridine 在 三烯丙基硼烷 、 sodium hydroxide 作用下， 生成 (2R,6S)-2-Allyl-6-methyl-1,2,3,6-tetrahydro-pyridine
  参考文献：
  名称：

  基于吡啶的还原反式-2,6-二烷基化反应制备反-顺-2-烯丙基-6-烷基（芳基）-1,2,3,6-四氢吡啶。(±)-表二氢吡啶和(±)-二氢吡啶的合成

  摘要：

  基于 RLi 与吡啶的 1,2-加成和三烯丙基硼烷的反式-6-烯丙基化的组合制备不对称反式-2-烯丙基-6-烷基（芳基）-1,2,3,6-四氢吡啶6的一般方法在甲醇的存在下进行了详细说明。结果表明，反式哌啶（6（R = Alk，Ph）在与三烯丙基硼烷一起加热时异构化为相应的顺式-2-烯丙基-6-烷基（苯基）-3-哌啶14，然后用甲醇和氨基硼烷（16）脱硼碱。化合物 6 和 14 的立体化学由二维 NOE 光谱测定。讨论了形成反式胺 6 及其转化为顺式异构体 14 的可能机制。生物碱 (±)-表二氢吡啶（反式 2-甲基-6-丙基哌啶 2a , 70%) 和 (±)-dihydropinidine (cis-2-methyl-6-propylpiperidine1d,

  DOI：

  10.1007/bf02495652
• 作为产物：
  描述：

  吡啶 、 三烯丙基硼烷 、 甲基锂 在 sodium hydroxide 作用下， 生成 trans-2-allyl-6-methyl-1,2,3,6-tetrahydropyridine
  参考文献：
  名称：

  基于吡啶的还原反式-2,6-二烷基化反应制备反-顺-2-烯丙基-6-烷基（芳基）-1,2,3,6-四氢吡啶。(±)-表二氢吡啶和(±)-二氢吡啶的合成

  摘要：

  基于 RLi 与吡啶的 1,2-加成和三烯丙基硼烷的反式-6-烯丙基化的组合制备不对称反式-2-烯丙基-6-烷基（芳基）-1,2,3,6-四氢吡啶6的一般方法在甲醇的存在下进行了详细说明。结果表明，反式哌啶（6（R = Alk，Ph）在与三烯丙基硼烷一起加热时异构化为相应的顺式-2-烯丙基-6-烷基（苯基）-3-哌啶14，然后用甲醇和氨基硼烷（16）脱硼碱。化合物 6 和 14 的立体化学由二维 NOE 光谱测定。讨论了形成反式胺 6 及其转化为顺式异构体 14 的可能机制。生物碱 (±)-表二氢吡啶（反式 2-甲基-6-丙基哌啶 2a , 70%) 和 (±)-dihydropinidine (cis-2-methyl-6-propylpiperidine1d,

  DOI：

  10.1007/bf02495652

文献信息

• New growth regulators of corn based on N-mono- and N,N-bis-3-butenyldichloroacetamides
  作者：Yu. N. Bubnov、Yu. Ya. Spiridonov、N. Yu. Kuznetsov

  DOI：10.1007/s11172-018-2080-0

  日期：2018.2

  Allylboration of imines, nitriles (including hydrocyanic acid), amides, lactams, aromatic azaheterocycles (pyridines, isoquinoline, and pyrrole) was used to synthesize a series of mono- and bis-3-butenylamines with different structures, which were converted to dichloroacetamides, new analogs of a known safener (herbicide antidote) Dichlormid successfully used in the cultivation of corn throughout the

  亚胺、腈（包括氢氰酸）、酰胺、内酰胺、芳香氮杂杂环（吡啶、异喹啉和吡咯）的烯丙基硼化被用于合成一系列不同结构的单-和双-3-丁烯胺，将其转化为二氯乙酰胺，一种已知安全剂（除草剂解毒剂）的新类似物二氯杀螨酯已成功用于世界各地的玉米种植。玉米种子发芽生物学试验表明，所得二氯乙酰胺大部分具有促生长活性，主要针对根系发育。化合物 2f、反式和顺式 2n、顺式 2s 和 2t 表现出出色的活性，超过敌草畏对玉米幼苗发育根系的刺激作用的 2 到 3 倍。
• Preparation of α-Acetonylpiperidines from α-Allylated Heterocycles by a Bromocyclocarbamation Reaction
  作者：Nikolai Yu. Kuznetsov、Victor N. Khrustalev、Ivan A. Godovikov、Yuri N. Bubnov

  DOI：10.1002/ejoc.200601031

  日期：2007.4

  2,6-Disubstituted (alkyl)(allyl)- and diallylpiperidines containing C=C bonds in different environments can be selectively transformed into α-acetonylpiperidines, including the alkaloid (±)-6-epipinidinone. The key step is the bromocyclocarbamation reaction of the N-Boc-protected α-allylheterocycle with N-bromosuccinimide. The bulky tert-butyl group on the piperidine ring can affect the diastereoselectivity

  在不同环境中含有 C=C 键的 2,6-二取代（烷基）（烯丙基）-和二烯丙基哌啶可以选择性地转化为 α-丙酮基哌啶，包括生物碱 (±)-6-epipinidinone。关键步骤是 N-Boc 保护的 α-烯丙基杂环与 N-溴代琥珀酰亚胺的溴环氨基甲酸酯化反应。哌啶环上庞大的叔丁基可通过 1,5-不对称诱导影响环化的非对映选择性。一种分离的非对映异构体的结构是通过 X 射线单晶衍射确定的。制备的双环溴化物很容易用 tBuOK 脱溴化氢，相应的烯醇被水解成 α-丙酮基哌啶盐酸盐。所提出的方法方便且易于执行。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Preparation of trans-2-allyl-6-alkyl(aryl)-1,2,3,6-tetrahydropyridines by reductive trans-2,6-dialkylation of pyridine. Synthesis of (±)-epidihydropinidine
  作者：Yuri N Bubnov、Elena V Klimkina、Anatoly V Ignatenko、Ilya D Gridnev

  DOI：10.1016/0040-4039(95)02383-6

  日期：1996.2

  A convenient method for the preparation of the title compounds involving the sequential treatment of pyridine with RLi (R = Alk, Ar), triallylborane and methanol is developed.

  开发了一种方便的制备标题化合物的方法，该方法涉及用RLi（R = Alk，Ar），三烯丙基硼烷和甲醇依次处理吡啶。
• ——
  作者：L. M. Korotayeva、T. Ya. Rubinskaya、E. V. Klimkina、V. P. Gultyai、Yu. N. Bubnov

  DOI：10.1023/a:1009580110623

  日期：——

  Electrochemical reduction of trans-2-allyl-6-R-1,2,3,6-tetrahydropyridines (R = Me, All, and Ph) on the mercury cathode in anhydrous DMF (with 0.1 M Bu4NClO4 as the supporting electrolyte) resulted in catalytic hydrogen evolution, while in the case of anhydrous DMF the electrochemical activity of the endocyclic double bond was dictated by the nature of the R substituent at the carbon atom neighboring the double bond. The electrocatalytic hydrogenation of the piperideines under study on the Ni (Ni-disp/Ni) cathode in 40%; aqueous DMF in the presence of a tenfold excess of AcOH yielded the corresponding trans-2-propyl-6-R-1 piperidines (R-1 = Me, Pr, acid Ph). Using trans-2,6-diallyl-1,2,3,6-tetrahydropyridine as an example, the conditions (with annealed copper as the cathode) for selective hydrogenation of the double bonds in allyl substituents with preservation of the endocyclic double bond were found.
• Preparative electroreduction oftrans-2-allyl-6-methyl(phenyl)-1,2,3,6-tetrahydropyridine
  作者：L. M. Korotayeva、T. Ya. Rubinskaya、E. V. Klimkina、V. P. Gultyai、Yu. N. Bubnov

  DOI：10.1007/bf02496263

  日期：1999.4

  Electrocatalytic hydrogenation of trans-2-allyl-6-phenyl-1,2,3,6-tetrahydropyridine and trans-2-allyl-6-methyl-1,2,3,6-tetrahydropyridine in 40% aqueous DMF in the presence of AcOH on a nickel cathode gave trans-6-phenyl-2-propylpiperidine and trans-2-methyl-6-propylpiperidine ((+/-)-epidihydropinidine), respectively. Direct electroreduction of trans-2-allyl-6-phenyl-1,2,3,6-tetrahydropyridine in anhydrous DMF on a mercury cathode afforded a 7 : 5 mixture of trans- and cis-2-allyl-6-phenylpiperidine. The structure of the latter compound was confirmed by 2D NOESY spectroscopy. The possible mechanism of formation of the cis-isomer is discussed.