1-benzyl-4-(bromomethyl)-3,3-dimethylpyrrolidin-2-one | 1050654-11-9

• 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-4-(bromomethyl)-3,3-dimethylpyrrolidin-2-one
• CAS: 1050654-11-9
• 化学式: C₁₄H₁₈BrNO
• 分子量: 296.207
• InChiKey: ZQYFSZHZUBFTHO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (1E)-N-Benzylprop-2-en-1-imine 在 barium titanate 、 copper(II) bis(trifluoromethanesulfonate) 、 三(2-吡啶基甲基)胺 、 三乙胺 作用下， 以 乙醚 、 氯仿 为溶剂， 反应 1.5h， 生成 1-benzyl-4-(bromomethyl)-3,3-dimethylpyrrolidin-2-one
  参考文献：
  名称：

  使用压电BaTiO3进行机电原子转移自由基环化反应。

  摘要：

  活性Cu I物种的形成和再生是铜催化原子转移自由基环化（ATRC）的基本机理步骤。通常，通过使用高Cu I催化剂负载量或添加还原性还原剂来确保反应混合物中催化活性Cu I物质的存在。在这项研究中，证明了如何通过机械球磨法利用钛酸钡（BaTiO 3）的压电特性在应变压电材料中引起电极化。这种策略可以将机械能转化为电能，从而将Cu II预催化剂还原为活性Cu I 铜催化的机械化学无溶剂ATRC反应中的所有物种。

  DOI：

  10.1002/anie.202003565

文献信息

• Cu⁰-Promoted Cyclisation of Unsaturated α-Halogeno Amides To Give β- and γ-Lactams
  作者：Andrew J. Clark、Jonathan N. Duckmanton、Fulvia Felluga、Armando Gennaro、Franco Ghelfi、Jack R. D. Hardiman、Abdirisak A. Isse、Claudia Manferdini、Domenico Spinelli

  DOI：10.1002/ejoc.201600249

  日期：2016.5

  Efficient 5-exo-trig atom-transfer radical cyclisation of 13 unsaturated α-halogeno amides mediated by Cu0 (copper wire) with tripyridylmethanimine ligand (TPMA; 1 mol-%) in a mixed solvent of EtOAc/EtOH (3:1) is reported (89–98 %), with recycling of the copper wire. A substantial improvement in conversion and selectivity was obtained when Na2CO3 (5 mol-%) was added to the reaction mixture. The Cu0

  在 EtOAc/EtOH (3:1) 的混合溶剂中，由 CuO（铜线）与三吡啶基甲亚胺配体（TPMA；1 mol-%）介导的 13 种不饱和 α-卤代酰胺的有效 5-exo-trig 原子转移自由基环化是报告 (89–98%)，回收铜线。当将 Na2CO3 (5 mol-%) 添加到反应混合物中时，转化率和选择性得到显着改善。CuO 在 SARA-ATRC 工艺中充当辅助活化剂和还原剂。该方案扩展到炔烃的环化和β-内酰胺的形成，尽管这些反应的产率较低（35-76%）。
• Engineered myoglobin as a catalyst for atom transfer radical cyclisation
  作者：Andriy Lubskyy、Chao Guo、Robert J. Chadwick、Alke Petri-Fink、Nico Bruns、Michela M. Pellizzoni

  DOI：10.1039/d2cc03227a

  日期：——

  able to perform atom transfer radical cyclisation reactions, i.e. intramolecular atom transfer radical additions. Replacing the iron-coordinating histidine with serine, or introducing small changes inside or at the entrance of the active site, transformed the completely inactive wild-type myoglobin into an artificial metalloenzyme able to catalyse the 5-exo cyclisation of halogenated unsaturated compounds

  肌红蛋白经过定点诱变并转化为能够进行原子转移自由基环化反应的催化剂，即。分子内原子转移自由基加成。用丝氨酸取代铁配位组氨酸，或在活性位点内部或入口处引入微小变化，将完全无活性的野生型肌红蛋白转化为能够催化卤代不饱和化合物5-外环化合成的人工金属酶γ-内酰胺。这种新颖的活性不仅可以通过纯化的蛋白质实现，而且可以在粗制细胞裂解物和全细胞中实现。
• 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.
• Copper mediated atom transfer radical cyclisations with AIBN
  作者：Andrew J. Clark、Paul Wilson

  DOI：10.1016/j.tetlet.2008.06.016

  日期：2008.8

  We have shown that it is possible to mediate a range of 5-exo trig and 5-exo dig atom transfer radical cyclisations of bromoacetamides using 0.1-1 mol % CuBr or CuBT2 in conjunction with 0.1-1 mol % tri(pyridin-2-ylmethyl)amine and 10 mol % AIBN. This equates to a 30-300-fold reduction in the amount of catalyst previously reported for these reactions and allows cyclisation to be carried out with the more oxidatively stable CuBr2 without the requirement of an inert atmosphere. (C) 2008 Elsevier Ltd. All rights reserved.
• Atom-transfer radical cyclization of α-bromocarboxamides under organophotocatalytic conditions
  作者：Naoki Tsuchiya、Yusei Nakashima、Goki Hirata、Takashi Nishikata

  DOI：10.1016/j.tetlet.2021.152952

  日期：2021.4