N-tosyl-2-(2-thienyl)ethylamine | 102996-95-2

• 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-tosyl-2-(2-thienyl)ethylamine
• 英文别名: N-<2-(2-Thienyl)ethyl>toluolsulfonamid；4-methyl-N-(2-(thiophen-2-yl)ethyl)benzenesulfonamide；4-Methyl-N-[2-(thiophen-2-yl)ethyl]benzene-1-sulfonamide；4-methyl-N-(2-thiophen-2-ylethyl)benzenesulfonamide
• CAS: 102996-95-2
• 化学式: C₁₃H₁₅NO₂S₂
• mdl: MFCD00176595
• 分子量: 281.4
• InChiKey: UMBGEZYIVHHOOZ-UHFFFAOYSA-N

物化性质

• 熔点：
  65 °C
• 沸点：
  436.7±55.0 °C(Predicted)
• 密度：
  1.261±0.06 g/cm3(Predicted)
• 溶解度：
  >42.2 [ug/mL]

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  82.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-tosyl-2-(2-thienyl)ethylamine 在 盐酸 、 sodium hydroxide 、 五氯化磷 、 potassium carbonate 、 红铝 、 tin(ll) chloride 作用下， 以 乙醇 、 溶剂黄146 、 1,2-二氯乙烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 28.5h， 生成 5,6,7,8-四氢-4H-噻吩并[2,3-d]氮杂
  参考文献：
  名称：

  5,6,7,8-四氢-4 H-噻吩并[2,3- d ]氮杂的新合成

  摘要：

  本文描述了从2-（2-噻吩基）乙胺或其N-（2-氯苄基）衍生物到5,6,7,8-四氢-4 H-噻吩并[2,3- d ]氮杂的两条新途径。这两个合成之一涉及从在位置4进行氯甲基化的6,7-二氢[3,2- c ]吡啶鎓衍生物进行的新环扩环。

  DOI：

  10.1002/jhet.5570220416
• 作为产物：
  描述：

  对甲苯磺酰氯 在 sodium azide 、 二氢吡啶 、 1,3-dicyano-5-fluoro-2,4,6-tris(diphenylamino)benzene 、 4-甲苯硫酚 作用下， 以 水 、 1,2-二氯乙烷 、 丙酮 为溶剂， 反应 10.0h， 生成 N-tosyl-2-(2-thienyl)ethylamine
  参考文献：
  名称：

  Organo‐Photocatalytic Anti‐Markovnikov Hydroamidation of Alkenes with Sulfonyl Azides: A Combined Experimental and Computational Study

  摘要：

  The construction of C(sp3)−N bonds via direct N‐centered radical addition with olefins under benign conditions is a desirable but challenging strategy. Herein, we describe an organo‐photocatalytic approach to achieve anti‐Markovnikov alkene hydroamidation with sulfonyl azides in a highly efficient manner under transition‐metal‐free and mild conditions. A broad range of substrates, including both activated and unactivated alkenes, are suitable for this protocol, providing a convenient and practical method to construct sulfonylamide derivatives. A synergistic experimental and computational mechanistic study suggests that the additive, Hantzsch ester (HE), might undergo a triplet‐triplet energy transfer manner to achieve photosensitization by the organo‐photocatalyst under visible light irradiation. Next, the resulted triplet excited state 3HE* could lead to a homolytic cleavage of C4−H bond, which triggers a straightforward H‐atom transfer (HAT) style in converting sulfonyl azide to the corresponding key amidyl radical. Subsequently, radical addition of the amidyl radical to alkenes followed by HAT from p‐toluenethiol could proceed to afford the desired anti‐Markovnikov hydroamidation product. It is worth noting that mechanistic pathway bifurcation could be possible for this reaction. A feasible radical chain propagation mechanistic pathway is also proposed to rationalize the high efficiency of this reaction.

  DOI：

  10.1002/anie.202406069

文献信息

• Direct Synthesis of α-Amino Nitriles from Sulfonamides via Base-Mediated C–H Cyanation
  作者：Shasha Shi、Xianyu Yang、Man Tang、Jiefeng Hu、Teck-Peng Loh

  DOI：10.1021/acs.orglett.1c01232

  日期：2021.5.21

  Herein, we disclose a transition-metal-free reaction system that enables α-cyanation of sulfonamides through C–H bond cleavage for the preparation of α-amino nitriles, including difficult-to-access all-alkyl α-tertiary scaffolds. More than 50 substrate examples prove a wide functional group tolerance. Additionally, its synthetic practicality is highlighted by gram-scalability and the late-stage modification

  在这里，我们公开了一种无过渡金属的反应体系，该体系可使磺酰胺通过C–H键断裂进行α-氰化，以制备α-氨基腈，包括难以接近的全烷基α-叔骨架。超过50个底物实例证明了广泛的官能团耐受性。另外，其合成实用性通过克可缩放性和天然化合物的后期修饰得到突出。机理实验表明，该过程涉及通过碱促进的HF的消除而原位形成亚胺中间体。
• Transition‐Metal‐Free α Csp ³ −H Cyanation of Sulfonamides
  作者：Liejin Zhou、Siqi Wei、Ziran Lei、Gangguo Zhu、Zuxiao Zhang

  DOI：10.1002/chem.202100902

  日期：2021.4.26

  site‐selective α‐functionalization of sulfonylamide derivatives through the in‐situ generation of imine intermediates. The N−F sulfonylamides, which could facilitate the elimination to generate imines, are coupled with TBACN to efficiently and mildly afford α‐amino cyanides. Comparing with Strecker reaction, this transformation offers a complementary strategy to efficiently construct α‐amino cyanides

  该报告描述了通过亚胺中间体的现场生成对磺酰胺衍生物进行的位点选择性α-官能化。可以促进消除反应生成亚胺的Nf磺酰胺与TBACN偶联，可有效，温和地提供α-氨基氰化物。与Strecker反应相比，这种转化提供了一种补充策略，可以从磺酰胺的直接αC-H官能化有效地构建α-氨基氰化物。该反应的特征还在于广泛的底物范围和无需快速色谱柱的后处理。更重要的是，通过控制离去基团产生亚胺的新的双电子途径使我们获得了出色的α位选择性。
• Regio- and Stereo-Selective Intermolecular Hydroamidation of Ynamides: An Approach to (<i>Z</i>)-Ethene-1,2-Diamides
  作者：Zhiyuan Peng、Zhenming Zhang、Yongliang Tu、Xianzhu Zeng、Junfeng Zhao

  DOI：10.1021/acs.orglett.8b02409

  日期：2018.9.21

  An efficient intermolecular trans-selective β-hydroamidation of ynamides to furnish a series of (Z)-ethene-1,2-diamide derivatives with excellent regio- and stereo-selectivities is described. The trans-β-addition reactions have been illustrated for a wide range of substrates and proceeded under basic reaction conditions using readily available materials in the absence of a transition-metal catalyst

  描述了有效的分子间反式β-氢化酰胺化酰胺，以提供一系列具有优异的区域和立体选择性的（Z）-乙烯-1,2-二酰胺衍生物。已经说明了广泛的底物的反式-β-加成反应，并且在不存在过渡金属催化剂的情况下，使用容易获得的材料在碱性反应条件下进行了反式-β-加成反应。这些新颖的（Z）-乙烯-1,2-二酰胺衍生物的合成方法为进一步探索其合成应用铺平了道路。
• NaI-Catalyzed Oxidative Amination of Aromatic Sodium Sulfinates: Synergetic Effect of Ethylene Dibromide and Air as Oxidants
  作者：Ying Fu、Quan-Zhou Li、Qin-Shan Xu、Helmut Hügel、Ming-Peng Li、Zhengyin Du

  DOI：10.1002/ejoc.201801386

  日期：2018.12.31

  A novel NaI-catalyzed oxidative amination of sodium sulfinates, employing both ethylene dibromide (EDB) and air as the oxidants, is described. EDB was first demonstrated to be a promising mild organic oxidant that in air, converted NaI into molecular iodine to promote the cross-coupling reactions of aromatic sodium sulfinates with amines to produce arylsulfonamides. Mechanistic studies indicated that

  描述了一种使用二溴化乙烯 (EDB) 和空气作为氧化剂的新型 NaI 催化亚磺酸钠氧化胺化。EDB 首次被证明是一种有前途的温和有机氧化剂，它在空气中将 NaI 转化为分子碘，以促进芳族亚磺酸钠与胺的交叉偶联反应，生成芳基磺酰胺。机理研究表明，反应过程中可能涉及自由基途径。
• Enantioselective Synthesis of <i>trans</i> -Vicinal Diamines <i>via</i> Rhodium-Catalyzed [2+2] Cycloaddition of Allenamides
  作者：Wei-Feng Zheng、Gui-Jun Sun、Liang Chen、Qiang Kang

  DOI：10.1002/adsc.201800021

  日期：2018.5.2

  An efficient protocol for the enantioselective Rh‐catalyzed intermolecular head‐to‐head [2+2] cycloaddition of allenamides was developed. A variety of enantio‐enriched cyclobutane‐1,2‐diamine derivatives were achieved in good yields with good to excellent enantioselectivities.

  开发了一种有效的方案，用于对映选择性的Rh催化的烯丙酰胺分子间头对头[2 + 2]环加成反应。以高收率获得了各种对映体富集的环丁烷1,2-二胺衍生物，并具有良好或优异的对映选择性。