N-2-bromobenzyl-5-allylpyrrolidin-2-one | 417699-93-5

• 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-2-bromobenzyl-5-allylpyrrolidin-2-one
• 英文别名: 5-allyl-1-(2-bromobenzyl)-pyrrolidin-2-one；1-[(2-Bromophenyl)methyl]-5-prop-2-enylpyrrolidin-2-one
• CAS: 417699-93-5
• 化学式: C₁₄H₁₆BrNO
• 分子量: 294.191
• InChiKey: PEECAEYZOJCGDW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  4
• 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

• 作为反应物：
  描述：

  N-2-bromobenzyl-5-allylpyrrolidin-2-one 在 palladium diacetate 、 palladium on activated charcoal potassium carbonate 、 三苯基膦 、 氢气 作用下， 以 N,N-二甲基甲酰胺 、 甲醇 为溶剂， 20.0~115.0 ℃ 、400.0 kPa 条件下， 反应 22.0h， 生成 10-methyl-2,3,5,10,11,11a-hexahydro-1H-azolo[1,2-a]benzo[e]azepin-3-one 、 10-methyl-2,3,5,10,11,11a-hexahydro-1H-azolo[1,2-a]benzo[e]azepin-3-one
  参考文献：
  名称：

  分子内 Heck 反应及吲哚齐酮、喹啉酮和苯并氮杂酮衍生物的合成

  摘要：

  N-烯丙基-、-芳基-或-苄基-5-烯丙基-2-吡咯烷酮和N-烯丙基-、-芳基-或-苄基-6-烯丙基-2-哌啶酮(1a f)的分子内Heck环化，制备通过烯丙基三甲基硅烷加成相应的环状 N-acyliminium 离子，以中等至良好的产率（56 90% ）。在所研究的所有实施例中都观察到了独家的外三键环化模式，并且伴随着双键迁移，这排除了我们与亲二烯体（如马来酸酐、甲基乙烯基）的一锅串联 Diels-Alder 环加成的尝试酮和偶氮二甲酸二乙酯。2:1 区域异构吲哚茚酮 5a-5b 混合物的催化加氢得到立体异构富集的顺式吲哚茚酮 6a (20: 1 混合物）的定量产率。在区域异构苯并氮杂酮 7b-8b 的催化氢化中观察到类似的行为。

  DOI：

  10.1055/s-2002-19293
• 作为产物：
  描述：

  N-(o-bromobenzyl)succinimide 在 bismuth(lll) trifluoromethanesulfonate 、 三乙基硼氢化锂 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 1.0h， 生成 N-2-bromobenzyl-5-allylpyrrolidin-2-one
  参考文献：
  名称：

  Intermolecular and Intramolecular α-Amidoalkylation Reactions Using Bismuth Triflate as the Catalyst

  摘要：

  Bismuth(III) triflate was found to promote the formation of stable cyclic N-acyliminium species in remarkable catalytic amounts (1 mol %). The alpha-amidoalkylation process seems to be effective in intermolecular and intramolecular manners leading to alpha-substituted lactams and heterocyclic systems containing azacycles, respectively. By comparing our results with those obtained with the classical Lewis acids as catalysts, it was evidenced clearly that the use of bismuth(III) triflate had been efficient for nearly all alpha-acetoxy lactams we used, except for N-acyliminium precursors bearing a sulfur atom. Also, the process seems to be easy, general, and clean, having diastereoselectivity comparable to protocols using classical Lewis acids and resulting in the formation of polyheterocyclic systems in good to excellent yields (64-99% in acetonitrile as solvent).

  DOI：

  10.1021/jo062077x

文献信息

• Intermolecular and Intramolecular α-Amidoalkylation Reactions Using Bismuth Triflate as the Catalyst
  作者：Frédéric Pin、Sébastien Comesse、Bernard Garrigues、Štefan Marchalín、Adam Daïch

  DOI：10.1021/jo062077x

  日期：2007.2.1

  Bismuth(III) triflate was found to promote the formation of stable cyclic N-acyliminium species in remarkable catalytic amounts (1 mol %). The alpha-amidoalkylation process seems to be effective in intermolecular and intramolecular manners leading to alpha-substituted lactams and heterocyclic systems containing azacycles, respectively. By comparing our results with those obtained with the classical Lewis acids as catalysts, it was evidenced clearly that the use of bismuth(III) triflate had been efficient for nearly all alpha-acetoxy lactams we used, except for N-acyliminium precursors bearing a sulfur atom. Also, the process seems to be easy, general, and clean, having diastereoselectivity comparable to protocols using classical Lewis acids and resulting in the formation of polyheterocyclic systems in good to excellent yields (64-99% in acetonitrile as solvent).
• The Intramolecular Heck Reaction and the Synthesis of Indolizidinone, Quinolizidinone and Benzoazepinone Derivatives
  作者：Ronaldo Pilli、Leonardo Santos

  DOI：10.1055/s-2002-19293

  日期：——

  N-allyl-, -aryl- or -benzyl-6- allyl-2-piperidinones ( 1a f), prepared through allyltrimethylsilane addition to the corresponding cyclic N-acyliminium ions, afforded indolizidinones (3a, 5a, 5b), quinolizidinones (3b, 4b) and ben- zoazepinones (7a, 8a, 7b, 8b) in moderate to good yields (56 90%). Exclusive exo-trig over endo-trig mode of cyclization was observed in all examples investigated, and it was

  N-烯丙基-、-芳基-或-苄基-5-烯丙基-2-吡咯烷酮和N-烯丙基-、-芳基-或-苄基-6-烯丙基-2-哌啶酮(1a f)的分子内Heck环化，制备通过烯丙基三甲基硅烷加成相应的环状 N-acyliminium 离子，以中等至良好的产率（56 90% ）。在所研究的所有实施例中都观察到了独家的外三键环化模式，并且伴随着双键迁移，这排除了我们与亲二烯体（如马来酸酐、甲基乙烯基）的一锅串联 Diels-Alder 环加成的尝试酮和偶氮二甲酸二乙酯。2:1 区域异构吲哚茚酮 5a-5b 混合物的催化加氢得到立体异构富集的顺式吲哚茚酮 6a (20: 1 混合物）的定量产率。在区域异构苯并氮杂酮 7b-8b 的催化氢化中观察到类似的行为。