N,N-dimethylthiocrotonic amide | 67797-21-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代酰胺
• 英文名称: N,N-dimethylthiocrotonic amide
• 英文别名: Buten-2-thiocarbonsaeure-dimethylamid；N,N-Dimethylbut-2-enethioamide；N,N-dimethylbut-2-enethioamide
• CAS: 67797-21-1
• 化学式: C₆H₁₁NS
• 分子量: 129.226
• InChiKey: MAXGSKFPNVWNSQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  35.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2(5H)-呋喃酮 、 N,N-dimethylthiocrotonic amide 在 tetrakis(actonitrile)copper(I) hexafluorophosphate 、 lithium 4-methoxyphenoxide 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 四氢呋喃 为溶剂， 生成 (S)-N,N-dimethyl-3-((R)-5-oxo-2,5-dihydrofuran-2-yl)butanethioamide
  参考文献：
  名称：

  不饱和丁内酯与α，β-不饱和硫代酰胺的直接催化不对称Vinylogous共轭加成

  摘要：

  软路易斯酸/布朗斯台德碱协同催化剂已使α，β-和β，γ-不饱和丁内酯直接催化不对称乙烯基共轭加成到α，β-不饱和硫代酰胺中，具有完美的原子经济性。当使用α-当归内酯及其衍生物作为亲核试剂时，低至0.5 mol％的催化剂负载量足以完成以高度非对映和对映选择性的方式构建连续的三和四取代的立体异构中心所必需的反应。

  DOI：

  10.1002/anie.201402332

文献信息

• Cooperative Activation of Alkyne and Thioamide Functionalities; Direct Catalytic Asymmetric Conjugate Addition of Terminal Alkynes to α,β-Unsaturated Thioamides
  作者：Ryo Yazaki、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1002/asia.201100050

  日期：2011.7.4

  revealed that the intermediate copper‐thioamide enolate functioned as a Brønsted base to generate copper alkynylide from the terminal alkyne, thus driving the catalytic cycle through an efficient proton transfer between substrates. These findings led to the identification of a more convenient catalyst using potassium hexamethyldisilazane (KHMDS) as the Brønsted base, which was particularly effective for

  详细描述了将末端炔烃直接催化不对称共轭加成至α，β-不饱和硫代酰胺的详细研究。一种柔软的路易斯酸/硬布朗斯台德碱协同催化剂，包含[Cu（CH 3 CN）4 ] PF 6，双膦配体和Li（OC 6 H 4 - p‐OMe）同时激活两种底物以补偿炔烃铜的低反应性。一系列控制实验表明，中间体铜硫代酰胺醇烯酸酯起布朗斯台德碱的作用，从末端炔烃生成炔烃铜，从而通过底物之间的有效质子转移驱动催化循环。这些发现导致鉴定了使用六甲基二硅氮烷钾（KHMDS）作为布朗斯台德碱的更方便的催化剂，该催化剂对于甲硅烷基乙炔的反应特别有效。硫酰胺官能团的不同转化以及GPR40受体激动剂AMG-837的简洁对映选择性合成突出了本催化方法的合成用途。
• Direct Catalytic Asymmetric Conjugate Addition of Saturated and Unsaturated Thioamides
  作者：Nilanjana Majumdar、Akira Saito、Liang Yin、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1021/acs.orglett.5b01644

  日期：2015.7.2

  Direct catalytic asymmetric conjugate addition of thiolactams to α,β-unsaturated thioamides was efficiently promoted by a soft Lewis acid/hard Brønsted base cooperative catalyst in a highly stereocontrolled manner. Thioamide functionality was crucial to promote both the efficient enolization of thiolactam pronucleophiles and the subsequent stereoselective conjugate addition to α,β-unsaturated thioamides

  柔软的路易斯酸/硬布朗斯台德碱协同催化剂以高度立体可控的方式有效地促进了硫内酰胺直接催化不对称共轭加成硫代内酰胺到α，β-不饱和硫代酰胺。硫酰胺功能对于促进硫内酰胺原亲核试剂的有效烯醇化和随后向α，β-不饱和硫代酰胺中立体选择性偶联物的添加至关重要。对产物的两种硫代酰胺官能团的不同操作突出了本催化体系的合成效用。
• Catalytic Asymmetric Conjugate Addition of Thiols to α,β‐Unsaturated Thioamides: Expeditious Access to Enantioenriched 1,5‐Benzothiazepines
  作者：Takanori Ogawa、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1002/anie.201204365

  日期：2012.8.20

  from commercially available reagents to afford the desired product in high enantioselectivity. The reaction was compatible with a free amino group, thus allowing for expeditious access to enantiomerically enriched 1,5‐benzothiazepines, which are important chemical entities in medicinal chemistry.

  轻柔地进行：标题反应在质子转移条件下用由市售试剂制备的催化剂进行，以高对映选择性提供所需产物。该反应与一个游离氨基相容，因此可以快速获得对映体富集的1,5-苯并噻嗪类，这是药物化学中的重要化学实体。
• Intermediate as Catalyst: Catalytic Asymmetric Conjugate Addition of Nitroalkanes to α,β-Unsaturated Thioamides
  作者：Takanori Ogawa、Shinsuke Mouri、Ryo Yazaki、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1021/ol202898e

  日期：2012.1.6

  Catalytic asymmetric conjugate addition of nitroalkanes to α,β-unsaturated thioamides is promoted by a mesitylcopper/(R)-DTBM-Segphos precatalyst, affording γ-nitrothioamides in moderate to high syn-selectivity and excellent enantioselectivity. The intermediate Cu-thioamide enolate functions as a soft Lewis acid/hard Brønsted base cooperative catalyst to drive the catalytic cycle efficiently under

  催化不对称共轭加成到硝基烷烃α，β不饱和硫代酰胺由mesitylcopper促进/（[R）-DTBM-SEGPHOS预催化剂，得到γ-nitrothioamides在中度至高度顺式-选择性和优良的对映选择性。中间的铜硫代酰胺醇烯酸酯充当软路易斯酸/硬布朗斯台德碱协作催化剂，以在质子转移条件下有效地驱动催化循环。
• Copper(I)‐Catalyzed Conjugate Addition/Enantioselective Protonation with Selenols and α‐Substituted α,β‐Unsaturated Thioamides
  作者：Hu Tian、Hong‐Ming Zhang、Liang Yin

  DOI：10.1002/anie.202301422

  日期：2023.6.12

  A copper(I)-catalyzed conjugate addition/enantioselective protonation with selenols and α-substituted α,β-unsaturated thioamides is disclosed, which affords a series of chiral selenides in high to excellent enantioselectivity.

  公开了铜 (I) 催化的与硒醇和 α-取代的 α,β-不饱和硫代酰胺的共轭加成/对映选择性质子化，它提供了一系列具有高对映选择性的手性硒化物。