N-allyl-N-((2E)-2-butenyl)-p-toluenesulfonamide | 952688-49-2

• 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-allyl-N-((2E)-2-butenyl)-p-toluenesulfonamide
• 英文别名: N-allyl-N-(2-butenyl)-p-toluenesulfonamide；N-[(E)-but-2-enyl]-4-methyl-N-prop-2-enylbenzenesulfonamide
• CAS: 952688-49-2
• 化学式: C₁₄H₁₉NO₂S
• 分子量: 265.376
• InChiKey: HVMPSRWFDLPXEQ-GQCTYLIASA-N

物化性质

• 沸点：
  375.8±52.0 °C(Predicted)
• 密度：
  1.094±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-allyl-N-((2E)-2-butenyl)-p-toluenesulfonamide 在 [(η⁶-p-cymene)RuCl(ind)(PCy3)]OTf 作用下， 以 氯苯 为溶剂， 反应 0.5h， 以95%的产率得到N-(对甲苯磺酰)-3-吡咯啉
  参考文献：
  名称：

  Allenylidene-to-Indenylidene Rearrangement in Arene−Ruthenium Complexes: A Key Step to Highly Active Catalysts for Olefin Metathesis Reactions

  摘要：

  The allenyliclene-ruthenium complexes [(eta(6)-arene)RuCl(=C=C=CR2)(PR'(3))]OTf (R-2 = Ph; fluorene, Ph, Me; PR'3 = PCY3, (PPr3)-Pr-i, PPh3) (OTf = CF3SO3) on protonation with HOTf at -40 degrees C are completely transformed into alkenylcarbyne complexes [(eta(6)-p-cymene)RuCl( CCH=CR2)(PR3)](OTf)(2). At -20 degrees C the latter undergo intramolecular rearrangement of the allenylidene ligand, with release of HOTf, into the indenylidene group in derivatives [(eta(6)-arene)RuCl(indenylidene)(PR3)]OTf. The in situ-prepared indenylidene- ruthenium complexes are efficient catalyst precursors for ring-opening metathesis polymerization of cyclooctene and cyclopentene, reaching turnover frequencies of nearly 300 s(-1) at room temperature. Isolation of these derivatives improves catalytic activity for the ring-closing metathesis of a variety of dienes and enynes. A mechanism based on the initial release of arene ligand and the in situ generation of the active catalytic species RuCI(OTf)(=CH2)(PR3) is proposed.

  DOI：

  10.1021/ja0579762
• 作为产物：
  描述：

  N-(叔丁氧羰基)对甲苯磺酰胺 在 potassium carbonate 、 三氟乙酸 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 41.5h， 生成 N-allyl-N-((2E)-2-butenyl)-p-toluenesulfonamide
  参考文献：
  名称：

  钌-卡宾催化剂和三甲基甲硅烷基乙烯基醚的结合促进了环化反应及其在杂环化合物：3-亚甲基-2,3-二氢吲哚和3-亚甲基-2,3-二氢苯并呋喃的合成中的应用。

  摘要：

  DOI：

  10.1002/anie.200454157

文献信息

• Regioselective Rh-Catalyzed Allylic Amination/Ring-Closing Metathesis Approach to Monocyclic Azacycles:  Diastereospecific Construction of 2,5-Disubstituted Pyrrolines
  作者：P. Andrew Evans、John. E. Robinson

  DOI：10.1021/ol991064l

  日期：1999.12.1

  [formula: see text] Regioselective rhodium-catalyzed allylic amination followed by ring-closing metathesis, using the Grubbs' catalyst, provides an expeditious route to monosubstituted azacycles. The enantiomerically enriched allylamine 1 can also be resubjected to the reaction sequence with (R)- and (S)-2b to facilitate the diastereospecific construction of 2,5-disubstituted pyrrolines 3/4.

  [公式：见正文]使用Grubbs的催化剂，区域选择性的铑催化的烯丙基胺化，然后进行闭环复分解，为单取代的氮杂环化合物提供了快速途径。也可以将对映体富集的烯丙胺1重新置于与（R）-和（S）-2b的反应序列中，以促进2，5-二取代的吡咯啉3/4的非对映特异性构建。
• Pd-Catalyzed Polymerization of Dienes that Involves Chain-Walking Isomerization of the Growing Polymer End: Synthesis of Polymers Composed of Polymethylene and Five-Membered-Ring Units
  作者：Takeshi Okada、Sehoon Park、Daisuke Takeuchi、Kohtaro Osakada

  DOI：10.1002/anie.200701630

  日期：2007.8.13
• Palladium-catalyzed cascade reactions of benzyl halides with N-allyl-N-(2-butenyl)-p-toluenesulfonamide
  作者：Yi-min Hu、Jie Zhou、Xiang-tian Long、Jian-lin Han、Chen-jian Zhu、Yi Pan

  DOI：10.1016/s0040-4039(03)01177-8

  日期：2003.6

  Reaction of benzyl halides with N-allyl-N-(2-butenyl)-p-toluenesulfonamide 1 in the presence of a palladium catalyst afforded dihydropyrroles 3 in moderate to excellent yields. It is proposed that the cyclic products were formed via a palladium-catalyzed cascade cyclization-coupling process. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Cycloisomerization Promoted by the Combination of a Ruthenium–Carbene Catalyst and Trimethylsilyl Vinyl Ether, and its Application in The Synthesis of Heterocyclic Compounds: 3-Methylene-2,3-dihydroindoles and 3-Methylene-2,3-dihydrobenzofurans
  作者：Yukiyoshi Terada、Mitsuhiro Arisawa、Atsushi Nishida

  DOI：10.1002/anie.200454157

  日期：2004.8.6
• Allenylidene-to-Indenylidene Rearrangement in Arene−Ruthenium Complexes: A Key Step to Highly Active Catalysts for Olefin Metathesis Reactions
  作者：Ricardo Castarlenas、Chloé Vovard、Cédric Fischmeister、Pierre H. Dixneuf

  DOI：10.1021/ja0579762

  日期：2006.3.1

  The allenyliclene-ruthenium complexes [(eta(6)-arene)RuCl(=C=C=CR2)(PR'(3))]OTf (R-2 = Ph; fluorene, Ph, Me; PR'3 = PCY3, (PPr3)-Pr-i, PPh3) (OTf = CF3SO3) on protonation with HOTf at -40 degrees C are completely transformed into alkenylcarbyne complexes [(eta(6)-p-cymene)RuCl( CCH=CR2)(PR3)](OTf)(2). At -20 degrees C the latter undergo intramolecular rearrangement of the allenylidene ligand, with release of HOTf, into the indenylidene group in derivatives [(eta(6)-arene)RuCl(indenylidene)(PR3)]OTf. The in situ-prepared indenylidene- ruthenium complexes are efficient catalyst precursors for ring-opening metathesis polymerization of cyclooctene and cyclopentene, reaching turnover frequencies of nearly 300 s(-1) at room temperature. Isolation of these derivatives improves catalytic activity for the ring-closing metathesis of a variety of dienes and enynes. A mechanism based on the initial release of arene ligand and the in situ generation of the active catalytic species RuCI(OTf)(=CH2)(PR3) is proposed.