3,3-dimethyl-4-methylene-1-(phenylmethyl)-2-pyrrolidinone

• 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: 3,3-dimethyl-4-methylene-1-(phenylmethyl)-2-pyrrolidinone
• 英文别名: 1-Benzyl-3,3-dimethyl-4-methylidenepyrrolidin-2-one
• 化学式: C₁₄H₁₇NO
• 分子量: 215.295
• InChiKey: MSKQEQDQSGIFCG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  苄基-2-丙炔胺 在 钾硼氢 、 Cu(tris(2-pyridylmethyl)amine)SO₄*5H₂O 、 三乙胺 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 4.66h， 生成 3,3-dimethyl-4-methylene-1-(phenylmethyl)-2-pyrrolidinone 、 3,3-dimethyl-4-bromomethylene-1-(phenylmethyl)-2-pyrrolidinone
  参考文献：
  名称：

  Atom-Transfer Cyclization with CuSO₄/KBH₄: A Formal “Activators Generated by Electron Transfer” Process Also Applicable to Atom-Transfer Polymerization

  摘要：

  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.

  DOI：

  10.1021/jo301429a

文献信息

• A versatile radical based synthesis of γ—lactams using nickel powder / acetic acid
  作者：Jean Boivin、Mohammed Yousfi、Samir Z. Zard

  DOI：10.1016/s0040-4039(00)77265-0

  日期：1994.8

  A variety of γ—lactams are obtained from suitable of α-haloamides by a radical cyclisation mediated by a combination of nickel powder and acetic acid.

  通过由镍粉和乙酸的组合介导的自由基环化，可以从合适的α-卤代酰胺中获得各种γ-内酰胺。
• 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 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.