N-benzyl-2-bromo-N-(cyclohex-1-enyl)-2-methylpropionamide | 254759-19-8

• 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: N-benzyl-2-bromo-N-(cyclohex-1-enyl)-2-methylpropionamide
• 英文别名: N-benzyl-2-methyl-2-bromo-N-cyclohexyl-1-enylpropionamide；N-benzyl-2,2-dimethyl-2-bromo-N-cyclohex-1-enylacetamide；N-benzyl-2-methyl-2-bromo-N-cyclohex-1-enylpropionamide；N-cyclohex-1-enyl-N-benzyl-2-bromo-2-methylpropionamide；N-benzyl-2-bromo-N-(cyclohexen-1-yl)-2-methylpropanamide
• CAS: 254759-19-8
• 化学式: C₁₇H₂₂BrNO
• 分子量: 336.272
• InChiKey: HWFURUQTDGKLEK-UHFFFAOYSA-N

物化性质

• 沸点：
  447.9±44.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-benzyl-2-bromo-N-(cyclohex-1-enyl)-2-methylpropionamide 在 JandaJel-supported (2-pyridyl)methanimine CuBr 作用下， 以 1,2-二氯乙烷 为溶剂， 以15%的产率得到1-benzyl-3,3-dimethyl-1,3-dihydro-indol-2-one
  参考文献：
  名称：

  Solid-Supported Copper Catalysts for Atom-Transfer Radical Cyclizations:  Assessment of Support Type and Ligand Structure on Catalyst Performance in the Synthesis of Nitrogen Heterocycles

  摘要：

  A range of solid supported pyridinemethanimine 9-11 and polyamine 12-15 ligands have been prepared on silica, polystyrene, and JandaJel supports. The CuCl and CuBr complexes of these supported ligands have been used to assess both the effect of the ligand type and the nature of the support upon a representative range of copper-mediated atom transfer 5-exo-trig 6, 24-25, 5-exo-dig 26, 4-exo-trig 28, and 5-endo-trig 27, 38 radical cyclizations to give nitrogen heterocycles. In addition, the effect of the nature of the support on the stereochemical outcome of the 5-exo cyclization of 25 has been probed. Generally, it was found that the type of support (e.g., polystyrene, silica, or JandaJel) had very little effect upon the efficiency and selectivity of the processes but that the nature of the ligand type immobilized was the important factor. Thus, the 5-exo cyclization of 6 and 24-26 proceeded more rapidly with the PMI ligands 9-11, whereas 4-exo cyclizations 28 and 5-endo, radical polar crossover reactions 27 and 38 proceeded more efficiently with the JJ-TEDETA ligand 15. The efficiency of the supported ligands was also compared to their solution counterparts 4 and 5. The reusability of P-PMDETA ligand system 13 was assessed in the cyclization of 6.

  DOI：

  10.1021/jo0521605
• 作为产物：
  描述：

  苄胺 在 N,N-二乙基苯胺 作用下， 以 甲苯 为溶剂， 生成 N-benzyl-2-bromo-N-(cyclohex-1-enyl)-2-methylpropionamide
  参考文献：
  名称：

  酰胺的键旋转动力学：5-Endo Trig自由基环化过程中酰基和手性转移势的影响

  摘要：

  已经通过可变温度NMR实验在不同溶剂中测量了一系列N-环烯基-N-苄基乙酰胺衍生物中N-烯基键旋转的障碍。阻挡层的范围为9.7至14.2 kcal / mol，这取决于乙酰胺酰基上的取代基。与非极性溶剂（例如甲苯）相比，诸如氯仿和甲醇之类的极性溶剂会增加旋转的障碍。估计了基于乙酰胺基的“模拟物”旋转的障碍。不同酰基的k rot值的相对顺序与其报道的Taft E s参数平行。在5- endo trig中成功进行手性转移 自由基环化，很明显，旋转速度必须比此处报道的旋转速度明显慢。

  DOI：

  10.1021/jo200343z

文献信息

• Atom-Transfer Radical Addition (ATRA) and Cyclization (ATRC) Reactions Catalyzed by a Mixture of [RuCl2Cp*(PPh3)] and Magnesium
  作者：Katrin Thommes、Burçak Içli、Rosario Scopelliti、Kay Severin

  DOI：10.1002/chem.200700442

  日期：2007.8.17

  A new catalytic procedure for atom-transfer radical addition (ATRA) and cyclization (ATRC) reactions is described. The combination of the ruthenium(III) complex [RuCl(2)Cp*(PPh3)] (Cp*: pentamethylcyclopentadienyl) with magnesium allows these reactions to be performed under mild conditions with high efficiency. In most cases, the catalyst concentrations required are significantly lower than those used

  描述了一种用于原子转移自由基加成（ATRA）和环化（ATRC）反应的新催化程序。钌（III）配合物[RuCl（2）Cp *（PPh3）]（Cp *：五甲基环戊二烯基）与镁的结合使这些反应可以在温和的条件下高效地进行。在大多数情况下，所需的催化剂浓度明显低于先前报道的程序中使用的浓度。建议镁充当还原剂，其产生和再生催化活性的钌（II）物种。通过X射线晶体学分析了前催化剂[RuCl（2）Cp *（PPh3）]。
• Atom-Transfer Cyclization with CuSO₄/KBH₄: A Formal “Activators Generated by Electron Transfer” Process Also Applicable to Atom-Transfer Polymerization
  作者：Andrew J. Clark、Alana E. C. Collis、David J. Fox、Lauren L. Halliwell、Natalie James、Rachel K. O’Reilly、Hemal Parekh、Andrew Ross、Andrew B. Sellars、Helen Willcock、Paul Wilson

  DOI：10.1021/jo301429a

  日期：2012.8.17

  The 4-exo and 5-exo-trig atom-transfer cyclizations of 1, 8a-e, 9, 12, and 13 can be mediated with as little as 0.05 mol % of Cu(TPMA)SO4 center dot 5H(2)O in the presence of 2.5 mol % of borohydride salts in 10 min at room temperature in air. This formal "activators generated by electron transfer" (AGET) procedure utilizes a cheap and oxidatively stable copper source (CuSO4 center dot 5H(2)O) and can be carried out in environmentally benign solvents (EtOH). It is possible to alter the product distribution in the 5-endo radical-polar crossover reactions of 10a,b and 11 by tailoring the amount of borohydride. Cyclization onto alkynes 14 and 15 is also possible in only 20 min. Controlled radical polymerization of styrene, with increased rates over conventional atom-transfer radical polymerization (ATRP), can be carried out in a controlled fashion (Mn, PDI) using either CuBr or CuSO4 center dot 5H(2)O and Bu4NBH4.
• Bond Rotation Dynamics of <i>N</i>-Cycloalkenyl-<i>N</i>-benzyl α-Haloacetamide Derivatives
  作者：David B. Guthrie、Krishnan Damodaran、Dennis P. Curran、Paul Wilson、Andrew J. Clark

  DOI：10.1021/jo900491w

  日期：2009.6.5

  Barriers to rotation of the N-alkenyl bond in a series of N-cycloalkenyl-N-benzyl alpha-haloacetamide derivatives have been measured by variable-temperature NMR experiments. The barriers range from 10 to 18 kcal/mol, depending on ring size and on substituents on the cycloalkene and the amide. The observed trends aid in the design of substituent combinations that provide resolvable enantiomers or diastereomers at ambient temperature. The compounds undergo 4-exo and 5-endo radical cyclizations at rates that may be faster or slower than the estimated rate of N-alkenyl bond rotation in the derived radicals, depending on the substituents.
• Efficient room temperature copper(I) mediated 5-endo radical cyclisations
  作者：Andrew J. Clark、Colin P. Dell、John M. Ellard、Nicola A. Hunt、John P. McDonagh

  DOI：10.1016/s0040-4039(99)01806-7

  日期：1999.12

  Reaction of bromo-enamides with catalytic Cu(Me-6-trien)Br at room temperature furnishes regioisomeric mixtures of unsaturated pyrrolidinones in a highly efficient manner via an initial 5-endo radical cyclisation reaction followed by an oxidation and elimination of H+. Bromo-enamide 3f furnishes the beta-lactam via a 4-exo cyclisation pathway. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Solid-Supported Catalysts for Atom-Transfer Radical Cyclization of 2-Haloacetamides
  作者：Andrew J. Clark、Robert P. Filik、David M. Haddleton、Arnaud Radigue、Christopher J. Sanders、Gerard H. Thomas、Mark E. Smith

  DOI：10.1021/jo9908896

  日期：1999.11.1