1-benzyl-2,3-diethyl-5-methyl-1,2-dihydropyridine | 1016970-53-8

• 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: 1-benzyl-2,3-diethyl-5-methyl-1,2-dihydropyridine
• 英文别名: 1-benzyl-2,3-diethyl-5-methyl-2H-pyridine
• CAS: 1016970-53-8
• 化学式: C₁₇H₂₃N
• 分子量: 241.376
• InChiKey: XCLYAHMEFSTATN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-benzyl-2,3-diethyl-5-methyl-1,2-dihydropyridine 在 palladium on activated charcoal air 、 氢气 作用下， 以 2,2,2-三氟乙醇 、 甲苯 为溶剂， 反应 24.0h， 以72 mg的产率得到2,3-diethyl-5-methylpyridine
  参考文献：
  名称：

  Synthesis of Dihydropyridines and Pyridines from Imines and Alkynes via C−H Activation

  摘要：

  A convenient one-pot C-H alkenylation/electrocyclization/aromatization sequence has been developed for the synthesis of highly substituted pyridine derivatives from alkynes and alpha,beta-unsaturated N-benzyl aldimines and ketimines that proceeds through dihydropyridine intermediates. A new class of ligands for C-H activation was developed, providing broader scope for the alkenylation step than could be achieved with previously reported ligands. Substantial information was obtained about the mechanism of the reaction. This included the isolation of a C-H activated complex and its structure determination by X-ray analysis; in addition, kinetic simulations using the Copasi software were employed to determine rate constants for this transformation, implicating facile C-H oxidative addition and slow reductive elimination steps.

  DOI：

  10.1021/ja7104784
• 作为产物：
  描述：

  (E)-N-benzyl-2-methylprop-2-en-1-imine 、 3-己炔 在 [RhCl(coe)2]2 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以97%的产率得到1-benzyl-2,3-diethyl-5-methyl-1,2-dihydropyridine
  参考文献：
  名称：

  Synthesis of Dihydropyridines and Pyridines from Imines and Alkynes via C−H Activation

  摘要：

  A convenient one-pot C-H alkenylation/electrocyclization/aromatization sequence has been developed for the synthesis of highly substituted pyridine derivatives from alkynes and alpha,beta-unsaturated N-benzyl aldimines and ketimines that proceeds through dihydropyridine intermediates. A new class of ligands for C-H activation was developed, providing broader scope for the alkenylation step than could be achieved with previously reported ligands. Substantial information was obtained about the mechanism of the reaction. This included the isolation of a C-H activated complex and its structure determination by X-ray analysis; in addition, kinetic simulations using the Copasi software were employed to determine rate constants for this transformation, implicating facile C-H oxidative addition and slow reductive elimination steps.

  DOI：

  10.1021/ja7104784

文献信息

• Synthesis of Isoquinuclidines from Highly Substituted Dihydropyridines via the Diels–Alder Reaction
  作者：Rhia M. Martin、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/ol303040r

  日期：2013.2.1

  A stereo- and regioselective Diels–Alder reaction for the synthesis of highly substituted isoquinuclidines from dihydropyridines and electron-deficient alkenes has been developed. While reactions with activated dienophiles proceed readily under thermal conditions, the use of Lewis acid additives is necessary to facilitate cycloadditions for less reactive alkenes. This procedure affords the target compounds

  已经开发出立体和区域选择性 Diels-Alder 反应，用于从二氢吡啶和缺电子烯烃合成高度取代的异奎宁环。虽然与活化的亲二烯体的反应在热条件下很容易进行，但必须使用路易斯酸添加剂来促进反应性较低的烯烃的环加成。该程序以高产率和非对映选择性提供目标化合物。
• Regio- and Stereoselective 1,2-Dihydropyridine Alkylation/Addition Sequence for the Synthesis of Piperidines with Quaternary Centers
  作者：Simon Duttwyler、Shuming Chen、Colin Lu、Brandon Q. Mercado、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1002/anie.201310517

  日期：2014.4.7

  example of C alkylation of 1,2‐dihydropyridines with alkyl triflates and Michael acceptors was developed to introduce quaternary carbon centers with high regio‐ and diastereoselectivity. Hydride or carbon nucleophile addition to the resultant iminium ion also proceeded with high diastereoselectivity. Carbon nucleophile addition results in an unprecedented level of substitution to provide piperidine rings

  开发了 1,​​2-二氢吡啶与烷基三氟甲磺酸酯和迈克尔受体的 C 烷基化的第一个例子，以引入具有高区域选择性和非对映选择性的季碳中心。氢化物或碳亲核试剂加成到所得亚胺离子也具有高非对映选择性。碳亲核试剂加成导致前所未有的取代水平，以提供具有相邻四取代碳原子的哌啶环。
• Stereoselective Alkylation of α,β-Unsaturated Imines via C−H Bond Activation
  作者：Denise A. Colby、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/ja0584931

  日期：2006.5.1

  alkylation of α,β-unsaturated imines via C−H activation followed by imine hydrolysis produces tri- and tetrasubstituted α,β-unsaturated aldehydes. In the presence of a rhodium catalyst, α,β-unsaturated N-benzyl imines derived from methacrolein, crotonaldehyde, and tiglic aldehyde undergo directed C−H activation at the β-position and react with terminal alkenes and alkynes to form the tri- and tetrasubstituted

  α,β-不饱和亚胺通过 CH 活化进行立体选择性烷基化，然后亚胺水解产生三和四取代的 α,β-不饱和醛。在铑催化剂存在下，衍生自异丁烯醛、巴豆醛和tiglic 醛的α,β-不饱和N-苄基亚胺在β-位进行定向C-H 活化，并与末端烯烃和炔烃反应形成三-和具有非常高立体选择性的四取代 α,β-不饱和亚胺。水解以提供 α,β-不饱和醛可以在保持β-烷基化亚胺产物立体化学的仔细控制的条件下进行。或者，对于甲基丙烯醛的 N-苄基亚胺的 β-烷基化产物，可以在提供完全异构化为 E 异构体的条件下进行水解。
• Synthesis of Dihydropyridines and Pyridines from Imines and Alkynes via C−H Activation
  作者：Denise A. Colby、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/ja7104784

  日期：2008.3.1

  A convenient one-pot C-H alkenylation/electrocyclization/aromatization sequence has been developed for the synthesis of highly substituted pyridine derivatives from alkynes and alpha,beta-unsaturated N-benzyl aldimines and ketimines that proceeds through dihydropyridine intermediates. A new class of ligands for C-H activation was developed, providing broader scope for the alkenylation step than could be achieved with previously reported ligands. Substantial information was obtained about the mechanism of the reaction. This included the isolation of a C-H activated complex and its structure determination by X-ray analysis; in addition, kinetic simulations using the Copasi software were employed to determine rate constants for this transformation, implicating facile C-H oxidative addition and slow reductive elimination steps.