2-benzyl-3,4,5,6-tetrahydropyridine | 95018-41-0

• 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: 2-benzyl-3,4,5,6-tetrahydropyridine
• 英文别名: 6-benzyl-2,3,4,5-tetrahydropyridine；2-benzyl-1-azacyclohexene
• CAS: 95018-41-0
• 化学式: C₁₂H₁₅N
• 分子量: 173.258
• InChiKey: CQYXMQAXMQKCMQ-UHFFFAOYSA-N

物化性质

• 沸点：
  277.2±19.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-benzyl-3,4,5,6-tetrahydropyridine 在 zinc chloride diethyl ether 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 20.0h， 生成 2-苄基哌啶
  参考文献：
  名称：

  Cp 2 TiMe 2催化的氨基炔的分子内加氢胺化/环化

  摘要：

  已经发现Cp 2 TiMe 2是氨基炔的分子内加氢胺化/环化的有效催化剂。在5.0 mol％Cp 2 TiMe 2的存在下，加氢胺化反应在100–110°C进行得很顺利，在4–6 h内可生成五元和六元环状亚胺。随后在室温下用锌改性的NaBH 3 CN还原后，可以良好的收率分离出环胺。

  DOI：

  10.1016/s0040-4039(02)00644-5
• 作为产物：
  描述：

  5-己炔-1-醇 在 copper(l) iodide 、 四(三苯基膦)钯 lithium aluminium tetrahydride 、 sodium azide 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 、 氘代苯 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 生成 2-benzyl-3,4,5,6-tetrahydropyridine
  参考文献：
  名称：

  Constrained Geometry Organoactinides as Versatile Catalysts for the Intramolecular Hydroamination/Cyclization of Primary and Secondary Amines Having Diverse Tethered C−C Unsaturation

  摘要：

  A series of "constrained geometry" organoactinide complexes, (CGC)An(NMe)(2) (CGC = Me2Si(eta(5)-Me4C5)((BuN)-Bu-t); An = Th, 1; U, 2), has been prepared via efficient in situ, two-step protodeamination routes in good yields and high purity. Both 1 and 2 are quantitatively converted to the neutrally charged, solvent-free dichlorides (1-Cl-2, 2-Cl-2) and slightly more soluble diiodides (1-I-2, 2-I-2) with excess Me3Si-X (X = Cl, I) in non-coordinating solvents. The new complexes were characterized by NMR spectroscopy, elemental analysis, and (for 1 and 2) single-crystal X-ray diffraction, revealing substantially increased metal coordinative unsaturation vs the corresponding Me2SiCp ''(2)AnR(2) (Cp '' = eta(5)-Me4C5; An = Th, R = CH2(SiMe3), 3; An = U, R = CH2Ph, 4) and Cp'(2)AnR(2) (Cp' = eta(5)-Me5C5 ; An = Th, R = CH2(SiMe3), 5; An = U, R = CH2(SiMe3), 6) complexes. Complexes 1-6 exhibit broad applicability for the intramolecular hydroamination of diverse C-C unsaturations, including terminal and internal aminoalkenes (primary and secondary amines), aminoalkynes (primary and secondary amines), aminoallenes, and aminodienes. Large turnover frequencies (N-t up to 3000 h(-1)) and high regioselectivities (>= 95%) are observed throughout, along with moderate to high diastereoselectivities (up to 90% trans ring closures). With several noteworthy exceptions, reactivity trends track relative 5f ionic radii and ancillary ligand coordinative unsaturation. Reactivity patterns and activation parameters are consistent with a reaction pathway proceeding via turnover-limiting CC/CC insertion into the An-N sigma-bond.

  DOI：

  10.1021/ja0665444

文献信息

• Amidate complexes of titanium and zirconium: a new class of tunable precatalysts for the hydroamination of alkynesElectronic supplementary information (ESI) available: experimental details. See http://www.rsc.org/suppdata/cc/b3/b304176j/
  作者：Chunyu Li、Robert K. Thomson、Bronwyn Gillon、Brian O. Patrick、Laurel L. Schafer

  DOI：10.1039/b304176j

  日期：——

  A series of bis(amidate)group 4-bis(amido) complexes have been prepared, characterized and have been shown to be highly tunable precatalysts for both the intra- and intermolecular hydroamination of alkynes.

  一系列含双（亚胺酸盐）的第4族双（酰胺）配合物已经被制备、表征，并显示出是高度可调的前催化剂，适用于炔烃的分子内和分子间氢胺化反应。
• Synthesis of bicyclic carbamates as precursors of Sedum alkaloid derivatives
  作者：Zsolt Szakonyi、Matthias D'hooghe、Iván Kanizsai、Ferenc Fülöp、Norbert De Kimpe

  DOI：10.1016/j.tet.2004.08.073

  日期：2005.2

  Synthesis of a N-Boc-protected piperidin-2-yl phosphine oxide starting from piperidine in three steps, followed by olefination using a variety of α,β-unsaturated aldehydes resulted in tert-butyl 2-(2′-alkenylidene)piperidine-1-carboxylates in high yields. A novel type of intramolecular cyclization of these enamides furnished a new family of 3-alkyl-4,6,7,8-tetrahydro-3H-pyrido[1,2-c][1,3]oxazin-1-ones

  从哌啶开始的三步合成N -Boc保护的哌啶-2-基氧化膦，然后使用多种α，β-不饱和醛进行烯化反应，生成2-（2'-烯叉基）哌啶叔丁基- 1-羧酸盐收率高。这些酰胺的新型分子内环化提供了一个新的3-烷基-4,6,7,8-四氢-3 H-吡啶基[1,2- c ] [1,3]恶嗪-1-酮家族。用于进一步加工的有用基材。随后使用NaCNBH 3或NaBH 4还原这些不饱和双环氨基甲酸酯，得到相应的3-烷基六氢吡啶基[1,2- c] [1,3]恶嗪-1-酮的立体选择性很高。两个代表的还原性开环以良好的产率提供了相应的景天生物碱衍生物。
• A Commercially Available and User-Friendly Catalyst for Hydroamination Reactions under Technical Conditions
  作者：Benjamin Zelenay、Peter Munton、Xiaojie Tian、Silvia Díez-González

  DOI：10.1002/ejoc.201900701

  日期：2019.8.7

  The activity of a simple, commercially available copper salt, [Cu(NCMe)4](BF4) in intramolecular hydroamination reactions of alkynes and allenes is presented. Reactions were successfully carried out in technical acetonitrile in the presence of air. While attempts of alkene hydroamination failed, this catalysts was also found active in intermolecular aza-Michael reactions.

  介绍了一种简单的市售铜盐 [Cu(NCMe)4](BF4) 在炔烃和丙二烯的分子内加氢胺化反应中的活性。在空气存在下，在工业乙腈中成功进行了反应。虽然烯烃加氢胺化的尝试失败了，但也发现这种催化剂在分子间氮杂-迈克尔反应中具有活性。
• An (<i>R</i>)-Imine Reductase Biocatalyst for the Asymmetric Reduction of Cyclic Imines
  作者：Shahed Hussain、Friedemann Leipold、Henry Man、Elizabeth Wells、Scott P. France、Keith R. Mulholland、Gideon Grogan、Nicholas J. Turner

  DOI：10.1002/cctc.201402797

  日期：2015.2

  enantiomerically pure chiral amines continues to expand, few existing methods provide access to secondary amines. To address this shortcoming, we have over-expressed the gene for an (R)-imine reductase [(R)-IRED] from Streptomyces sp. GF3587 in Escherichia coli to create a recombinant whole-cell biocatalyst for the asymmetric reduction of prochiral imines. The (R)-IRED was screened against a panel of cyclic imines

  尽管可用于合成对映体纯的手性胺的生物催化剂的范围不断扩大，但现有的方法很少能提供仲胺的途径。为了解决这个缺点，我们过量表达了链霉菌属（Streptomyces sp。）的（R）-亚胺还原酶[（R）-IRED]的基因。GF3587在大肠杆菌中创建重组全细胞生物催化剂，用于不对称还原前手性亚胺。针对一组环状亚胺和两个亚胺离子筛选了（R）-IRED，结果显示该催化剂具有较高的催化活性和对映选择性。从亚胺前体的制备规模的生物碱（R）-亚氨酸的合成规模（90％收率； 99％ee）以克为单位进行。酶活性位点的同源模型，基于来自链霉菌的紧密相关的（R）-IRED的结构，
• Catalytic Asymmetric Synthesis of Morpholines. Using Mechanistic Insights To Realize the Enantioselective Synthesis of Piperazines
  作者：Ying Yin Lau、Huimin Zhai、Laurel L. Schafer

  DOI：10.1021/acs.joc.6b01884

  日期：2016.10.7

  and practical catalytic approach for the enantioselective synthesis of 3-substituted morpholines through a tandem sequential one-pot reaction employing both hydroamination and asymmetric transfer hydrogenation reactions is described. Starting from ether-containing aminoalkyne substrates, a commercially available bis(amidate)bis(amido)Ti catalyst is utilized to yield a cyclic imine that is subsequently

  描述了一种有效且实用的催化方法，该方法通过使用氢化胺化反应和不对称转移氢化反应的串联顺序一锅反应，对映选择性合成3-取代的吗啉。从含醚的氨基炔烃底物开始，使用市售的双（氨基甲酸酯）双（酰胺基）Ti催化剂产生环状亚胺，然后使用Noyori–Ikariya催化剂RuCl [（S，S）-Ts-DPEN进行还原]（η 6 - p-cymene），以高收率得到对映体3-取代的吗啉，对映体过量> 95％。宽泛的官能团是可以容忍的。底物范围的研究表明，含醚底物主链中的氧与Ru催化剂的[（S，S）-Ts-DPEN]配体之间的氢键相互作用对于获得高ee至关重要。这种见解导致了预测所观察到的绝对立体化学的机械提议。最重要的是，这种机理上的见解使该策略得以扩展，以包括N作为可以结合到基质中的替代氢键受体。因此，还证明了3-取代的哌嗪的催化，对映选择性合成。