(2E)-N-(3-formyl-2-propenyl)-N-(2-propynyl)tosylamide | 384836-87-7

• 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: (2E)-N-(3-formyl-2-propenyl)-N-(2-propynyl)tosylamide
• 英文别名: 4-methyl-N-[(E)-4-oxobut-2-enyl]-N-prop-2-ynylbenzenesulfonamide
• CAS: 384836-87-7
• 化学式: C₁₄H₁₅NO₃S
• 分子量: 277.344
• InChiKey: DKSUGVBIEKLSDU-SNAWJCMRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  62.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2E)-N-(3-formyl-2-propenyl)-N-(2-propynyl)tosylamide 在 cesium fluoride 作用下， 以 乙二醇二甲醚 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 4-(2,2,2-trifluoro-1-hydroxyethyl)-2-tosyl-2,3,3a,4-tetrahydro-1H-cyclopenta[c]pyrrol-5-one
  参考文献：
  名称：

  Scope and limitation of intramolecular Pauson–Khand reaction of fluorine-containing enynes

  摘要：

  Intramolecular Pauson-Khand reaction of various fluorine-containing enynes was investigated under various conditions. The reaction of the substrates. which have fluorine atom(s) or fluorine-containing group(s) attached to alkenyl moiety, gave the corresponding cyclopentenones in low to moderate yield, while that of the substrates bearing fluorine-containing groups attached to alkynyl moiety afforded the corresponding cyclopentenones in low to high yield. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-1139(01)00436-5
• 作为产物：
  描述：

  4-Methyl-N-(2-oxoethyl)-N-(prop-2-yn-1-yl)benzenesulfonamide 在 sodium hydride 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 2.17h， 生成 (2E)-N-(3-formyl-2-propenyl)-N-(2-propynyl)tosylamide
  参考文献：
  名称：

  Scope and limitation of intramolecular Pauson–Khand reaction of fluorine-containing enynes

  摘要：

  Intramolecular Pauson-Khand reaction of various fluorine-containing enynes was investigated under various conditions. The reaction of the substrates. which have fluorine atom(s) or fluorine-containing group(s) attached to alkenyl moiety, gave the corresponding cyclopentenones in low to moderate yield, while that of the substrates bearing fluorine-containing groups attached to alkynyl moiety afforded the corresponding cyclopentenones in low to high yield. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-1139(01)00436-5

文献信息

• Rhodium-Catalyzed Intra- and Intermolecular [5 + 2] Cycloaddition of 3-Acyloxy-1,4-enyne and Alkyne with Concomitant 1,2-Acyloxy Migration
  作者：Xing-Zhong Shu、Xiaoxun Li、Dongxu Shu、Suyu Huang、Casi M. Schienebeck、Xin Zhou、Patrick J. Robichaux、Weiping Tang

  DOI：10.1021/ja2109097

  日期：2012.3.21

  type of rhodium-catalyzed [5 + 2] cycloaddition was developed for the synthesis of seven-membered rings with diverse functionalities. The ring formation was accompanied by a 1,2-acyloxy migration event. The five- and two-carbon components of the cycloaddition are 3-acyloxy-1,4-enynes (ACEs) and alkynes, respectively. Cationic rhodium(I) catalysts worked most efficiently for the intramolecular cycloaddition

  开发了一种新型的铑催化 [5 + 2] 环加成反应，用于合成具有多种功能的七元环。环的形成伴随着 1,2-酰氧基迁移事件。环加成的五碳和二碳组分分别是 3-酰氧基-1,4-烯炔 (ACE) 和炔烃。阳离子铑（I）催化剂对分子内环加成最有效，而只有中性铑（I）配合物才能促进分子间反应。在这两种情况下，缺电子的亚磷酸酯或膦配体通常可以提高环加成的效率。在分子内和分子间反应中研究了 ACE 和炔烃的范围。由此产生的七元环产物具有三个可以选择性功能化的双键。
• Transfer of Chirality in the Rhodium-Catalyzed Intramolecular [5+2] Cycloaddition of 3-Acyloxy-1,4-enynes (ACEs) and Alkynes: Synthesis of Enantioenriched Bicyclo[5.3.0]decatrienes
  作者：Xing-zhong Shu、Casi M. Schienebeck、Wangze Song、Ilia A. Guzei、Weiping Tang

  DOI：10.1002/anie.201306919

  日期：2013.12.16

  Chiral bicycles: Enantioenriched bicyclo[5.3.0]decatrienes were prepared from readily available chiral 3‐acyloxy‐1,4‐enynes (ACEs) for the first time. In most cases, the chirality of the ACEs could be transferred to the bicyclic products with high efficiency. Inversion of the configuration was observed, thus confirming the predictions of previous computational studies.

  手性自行车：首次从现成的手性 3-酰氧基-1,4-烯炔 (ACE) 制备对映体富集的双环 [5.3.0] 癸三烯。在大多数情况下，ACE 的手性可以高效地转移到双环产品中。观察到配置的反转，从而证实了先前计算研究的预测。
• Platinum-Catalyzed Cycloisomerization Reaction of 1,6-Enyne Coupling with Rearrangement of Propargylic Esters
  作者：Li Lu、Xue-Yuan Liu、Xing-Zhong Shu、Ke Yang、Ke-Gong Ji、Yong-Min Liang

  DOI：10.1021/jo802043z

  日期：2009.1.2

  A platinum-catalyzed cycloisomerization of 1,6-enyne coupling with the rearrangement chemistry of propargylic ester has been developed. Most probably, under platinum catalysis, propargylic ester undergoes the 1,3-acyloxy migration to afford metal allene intermediate, which is followed by the Diels-Alder-type reaction. 1,3-Acyloxy migration is the key step during the transformation.
• Two Manifolds for Metal-Catalyzed Intramolecular Diels–Alder Reactions of Unactivated Alkynes
  作者：Alois Fürstner、Christopher C. Stimson

  DOI：10.1002/anie.200703321

  日期：2007.11.26
• Scope and limitation of intramolecular Pauson–Khand reaction of fluorine-containing enynes
  作者：Miyuki Ishizaki、Daisuke Suzuki、Osamu Hoshino

  DOI：10.1016/s0022-1139(01)00436-5

  日期：2001.9

  Intramolecular Pauson-Khand reaction of various fluorine-containing enynes was investigated under various conditions. The reaction of the substrates. which have fluorine atom(s) or fluorine-containing group(s) attached to alkenyl moiety, gave the corresponding cyclopentenones in low to moderate yield, while that of the substrates bearing fluorine-containing groups attached to alkynyl moiety afforded the corresponding cyclopentenones in low to high yield. (C) 2001 Elsevier Science B.V. All rights reserved.