(E)-N-methyl-N-(4-phenylbut-3-en-1-yn-1-yl)methanesulfonamide | 1562381-11-6

• 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: (E)-N-methyl-N-(4-phenylbut-3-en-1-yn-1-yl)methanesulfonamide
• 英文别名: N-methyl-N-[(E)-4-phenylbut-3-en-1-ynyl]methanesulfonamide
• CAS: 1562381-11-6
• 化学式: C₁₂H₁₃NO₂S
• 分子量: 235.307
• InChiKey: LGCBNFDZAZKALW-UXBLZVDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  (E)-N-methyl-N-(4-phenylbut-3-en-1-yn-1-yl)methanesulfonamide 在 三氟甲磺酸三甲基硅酯 、 氢溴酸 、 zinc trifluoromethanesulfonate 、 二异丙胺 、 zinc dibromide 作用下， 以 二氯甲烷 、 水 、 1,2-二氯乙烷 为溶剂， 反应 5.75h， 生成 N-(4-bromo-5-phenylfuran-2-yl)-N,4-dimethylbenzenesulfonamide
  参考文献：
  名称：

  Zn(II)- or Ag(I)-Catalyzed 1,4-Metathesis Reactions between 3-En-1-ynamides and Nitrosoarenes

  摘要：

  Catalyst-dependent metathesis reactions between 3-en-1-ynamides and nitrosoarenes are described. Particularly notable are the unprecedented 1,4-metathesis reactions catalyzed by Ag(I) or Zn(II) to give 2-propynimidamides and benzaldehyde derivatives. With 3-en-1-ynamides bearing a cycloalkenyl group, 1,4-oxoimination products were produced efficiently. We have developed metathesis/alkynation cascades for unsubstituted 2-propynimidamides and benzaldehyde species generated in situ, to manifest 1,4-hydroxyimination reactions of 3-en-1-ynes. Both 1,4-oxoiminations and 1,4-hydroxyiminations increase the molecular complexity of products.

  DOI：

  10.1021/ja412634w
• 作为产物：
  描述：

  (E)-but-1-en-3-yn-1-ylbenzene 在 N-溴代丁二酰亚胺(NBS) 、 1,10-菲罗啉 、 copper(ll) sulfate pentahydrate 、 potassium carbonate 、 silver nitrate 作用下， 以 丙酮 、 甲苯 为溶剂， 反应 1.0h， 生成 (E)-N-methyl-N-(4-phenylbut-3-en-1-yn-1-yl)methanesulfonamide
  参考文献：
  名称：

  Zn(II)- or Ag(I)-Catalyzed 1,4-Metathesis Reactions between 3-En-1-ynamides and Nitrosoarenes

  摘要：

  Catalyst-dependent metathesis reactions between 3-en-1-ynamides and nitrosoarenes are described. Particularly notable are the unprecedented 1,4-metathesis reactions catalyzed by Ag(I) or Zn(II) to give 2-propynimidamides and benzaldehyde derivatives. With 3-en-1-ynamides bearing a cycloalkenyl group, 1,4-oxoimination products were produced efficiently. We have developed metathesis/alkynation cascades for unsubstituted 2-propynimidamides and benzaldehyde species generated in situ, to manifest 1,4-hydroxyimination reactions of 3-en-1-ynes. Both 1,4-oxoiminations and 1,4-hydroxyiminations increase the molecular complexity of products.

  DOI：

  10.1021/ja412634w

文献信息

• General Entry into <i>o</i> -,<i>o′</i> -Heteroatom-Linked <i>N</i> -(Hetero)aryl-Imidazole Motifs by Gold-Catalysed Formal [3+2]-Dipolar Cycloaddition
  作者：Miguel Garzón、Elsa M. Arce、Raju Jannapu Reddy、Paul W. Davies

  DOI：10.1002/adsc.201700249

  日期：2017.6.6

  general redox‐neutral approach into the o‐,o′‐heteroatom‐linked N‐(hetero)aryl‐imidazole family of heteroaromatics has been developed. New types of heteroatom substituted carbimidoyl nitrenoids are efficiently realised from robust, bench‐stable N‐(heteroaryl)‐pyridinium‐N‐aminides by formal gold‐catalysed [3+2]‐dipolar cycloadditions across ynamides. Broad structural variety and functional group tolerance

  已开发出一种将杂芳烃的邻，邻杂原子连接的N-（杂）芳基-咪唑家族的氧化还原中性方法。新型的杂原子取代的碳酰亚胺基亚硝基化合物可以通过稳定的，稳定的N-（杂芳基）-吡啶鎓-N-胺类化合物，通过正式的金催化的[3 + 2]-偶极环加成酰胺类有效地实现。广泛的结构多样性和官能团耐受性允许快速进入各种功能化的支架，如制备8个不同的杂芳族核心所示。
• Gold-Catalyzed Imination/Mannich Reaction Cascades of 3-En-1-ynamides with Anilines and Aldehydes to Enable 1,5-Nitrogen Functionalizations
  作者：RahulKumar Rajmani Singh、Rai-Shung Liu

  DOI：10.1002/adsc.201600072

  日期：2016.4.28

  Gold‐catalyzed imination/Mannich reaction cascades on readily available 3‐en‐1‐ynamides enable the diastereoselective synthesis of 1,5‐iminoamino compounds in a one‐pot operation. The reactions work well with diversified 3‐en‐1‐ynamides, aldehydes and anilines with good to excellent diastereoselectivities. Our control experiments indicate gold‐catalyzed aminations of 3‐en‐1‐ynamides to yield α‐imino

  金催化的亚胺/曼尼希反应在易于使用的3烯1酰胺上进行级联，可在一锅操作中非对映选择性地合成1,5-亚氨基氨基化合物。该反应可与具有良好或优异的非对映选择性的多样化3-1-1-酰胺，醛和苯胺一起使用。我们的对照实验表明，金催化的3-en-1-酰胺的胺化反应可生成α-亚氨基烯丙基金的中间体，这些中间体随后可与亚胺反应，选择性地实现曼尼希反应。该反应继续进行抗那些-3-烯-1- ynamides轴承无环烯烃，而-选择性顺他们的基于环烯烃的类似物具有选择性。开放过渡态可以基于反平面构象令人满意地合理化这些观察到的立体选择性。
• Regiocontrolled Gold-Catalyzed [2+2+2] Cycloadditions of Ynamides with Two Discrete Nitriles to Construct 4-Aminopyrimidine Cores
  作者：Somnath Narayan Karad、Rai-Shung Liu

  DOI：10.1002/anie.201405312

  日期：2014.8.18

  Reported herein is the novel gold‐catalyzed intermolecular [2+2+2] cycloaddition of ynamides with two discrete nitriles to form monomeric 4‐aminopyrimidines, which are pharmaceutically important structural motifs. The utility of this new cycloaddition is demonstrated by the excellent regioselectivity obtained using a variety of ynamides and nitriles.

  本文报道的是新型的金催化的酰胺类分子间[2 + 2 + 2]分子间环加成反应，形成两个离散的腈基，形成单体的4-氨基嘧啶，这是药学上重要的结构基序。通过使用多种酰胺和腈获得的优异的区域选择性证明了这种新的环加成反应的实用性。
• Hetero-Tetradehydro-Diels–Alder Cycloaddition of Enynamides and Cyanamides: Gold-Catalyzed Generation of Diversely Substituted 2,6-Diaminopyridines
  作者：Nikolay V. Shcherbakov、Dmitry V. Dar’in、Vadim Yu. Kukushkin、Alexey Yu. Dubovtsev

  DOI：10.1021/acs.joc.1c00558

  日期：2021.5.21

  hetero-tetradehydro-Diels–Alder cycloaddition of enynamides and cyanamides comprises an efficient route to diversely substituted 2,6-diaminopyridines (28 examples; yields up to 99%). The reaction proceeds under very mild conditions (DCM, rt) with high functional group tolerance. The obtained 2,6-diaminopyridines represent a useful synthetic platform with an easily modulated substitution pattern for subsequent

  金（I）催化的乙酰胺和氰酰胺杂四-脱氢-狄尔斯-阿尔德环加成反应是制备不同取代的2,6-二氨基吡啶的有效途径（28个实例；产率高达99％）。反应在具有高官能团耐受性的非常温和的条件下（DCM，rt）进行。所获得的2，6-二氨基吡啶代表有用的合成平台，其具有易于调节的取代模式，用于吡啶核和N-取代基的随后官能化。
• (IPr)CuF-catalyzed α-site regiocontrolled trans-hydrofluorination of ynamides
  作者：Guohao Zhu、Shineng Qiu、Yang Xi、Yao Ding、Dongming Zhang、Rong Zhang、Guangke He、Hongjun Zhu

  DOI：10.1039/c6ob01345g

  日期：——

  With Et3N·3HF as the fluorination reagent, (IPr)CuF-catalyzed α-site regiocontrolled trans-hydrofluorination of ynamides has been achieved, affording (Z)-α-fluoroenamides in moderate to excellent yields. It was interesting to note that the regioselectivity of the reaction is reversed to that observed in the (Ph3P)3CuF-catalyzed hydrofluorination of ynamides. Additionally, a variety of different ynamides

  以Et 3 N·3HF为氟化剂，可以实现（IPr）CuF催化的α-位点区域控制的酰胺的反式-氢氟化，从而以中等至极好的收率得到（Z）-α-氟代酰胺。有趣的是，该反应的区域选择性与在（Ph 3 P）3 CuF催化的乙酰胺的氢氟化反应中观察到的相反。另外，包括恶唑烷二酰基-，咪唑基-和N-磺酰基乙酰胺在内的多种不同的乙酰胺适合于反应体系，并且随后氟化产物的氧化使得能够方便地合成为α-氟酰亚胺。