(E)-1-(2-thioxothiazolidin-3-yl)but-2-en-1-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (E)-1-(2-thioxothiazolidin-3-yl)but-2-en-1-one
• 英文别名: 3-((2E)-butenoyl)-4-thiazolidine-2-thione；3-crotonoyl-2-thiazolidinethione；N-crotonylthiazolidinethione；Crotonylthiazolidinethione；(E)-1-(2-sulfanylidene-1,3-thiazolidin-3-yl)but-2-en-1-one
• 化学式: C₇H₉NOS₂
• 分子量: 187.287
• InChiKey: MQUKLHYHIWJFPP-NSCUHMNNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  77.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-巯基噻唑啉 、 (E)-1-(2-thioxothiazolidin-3-yl)but-2-en-1-one 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以80%的产率得到1,3-Bis(2-sulfanylidene-1,3-thiazolidin-3-yl)butan-1-one
  参考文献：
  名称：

  Oxazolidine-2-thiones and Thiazolidine-2-thiones as Nucleophiles in Intermolecular Michael Additions

  摘要：

  Conjugate addition of thiazolidinethiones and oxazolidinethiones to N-crotonylthiazolidinethiones and -oxazolidinethiones was observed in the presence of excess triethylamine in dichloromethane. The addition takes place by the nitrogen of the heterocycle with high diastereoselectivity. It was observed that the stereoselective addition occurs on the anti-s-cis conformation of the N-enoyl sulfur-containing heterocycle.

  DOI：

  10.1021/ol301489y
• 作为产物：
  描述：

  2-巯基噻唑啉 、 2-丁烯酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 生成 (E)-1-(2-thioxothiazolidin-3-yl)but-2-en-1-one
  参考文献：
  名称：

  Oxazolidine-2-thiones and Thiazolidine-2-thiones as Nucleophiles in Intermolecular Michael Additions

  摘要：

  Conjugate addition of thiazolidinethiones and oxazolidinethiones to N-crotonylthiazolidinethiones and -oxazolidinethiones was observed in the presence of excess triethylamine in dichloromethane. The addition takes place by the nitrogen of the heterocycle with high diastereoselectivity. It was observed that the stereoselective addition occurs on the anti-s-cis conformation of the N-enoyl sulfur-containing heterocycle.

  DOI：

  10.1021/ol301489y

文献信息

• Bis(oxazoline)copper(II) complexes as chiral catalysts for the enantioselective Diels-Alder reaction
  作者：David A. Evans、Scott J. Miller、Thomas Lectka

  DOI：10.1021/ja00067a091

  日期：1993.7

  observations on the utility of chiral Cu(1I) bis(oxazoline) complexes as Lewis acids in the catalysis of these reactions. Attractive attributes of this catalyst system include an expanded scope of utilizable dienophiles and a clearly interpretable geometry for the catalyst-dienophile complex which rationalizes the sense of asymmetric induction for the cycloaddition process.

  Cz 对称双（恶唑啉）铜配合物已被证明是对映选择性烯烃环丙烷化 2 和氮丙啶化反应的出色催化剂。 3 此外，Corey 证明了这些配体的 Mg（I1）和 Fe（II1）配合物 4 作为手性路易斯酸催化剂的前景未取代丙烯酰亚胺的 Diels-Alder 反应。本次通讯的目的是报告我们对手性 Cu(1I) 双（恶唑啉）配合物作为路易斯酸在这些反应的催化中的效用的观察结果。该催化剂体系的吸引人的属性包括可利用的亲二烯体的扩大范围和催化剂-亲二烯体复合物的清晰可解释的几何形状，这使环加成过程的不对称感应合理化。
• DMAP-promoted racemization-free deacylation of carboxthioimide† adducts: carboxthioimide as a versatile carboxy protecting group
  作者：Dah-Wei Su、Ying-Chuan Wang、Tu-Hsin Yan

  DOI：10.1039/a900577c

  日期：——

  The DMAP-promoted deacylation of carboxthioimide adducts can be directed to form either acid or various ester protecting groups with no detectable levels of epimerization.

  DMAP促进的羧基硫亚胺加成物去酰化反应可以定向生成酸或各种酯保护基，且没有检测到明显的叠氢化现象。
• Bis(imine)-copper(II) complexes as chiral lewis acid catalysts for the Diels-Alder reaction
  作者：David A. Evans、Thomas Lectka、Scott J. Miller

  DOI：10.1016/s0040-4039(00)61588-5

  日期：1993.10

  We report the Diels-Alder reactions of imide-derived dienophiles 2a–2d and 4b–4d with cyclopentadiene catalysed by square-planar Cu(OTf)2-bis(imine) complexes. The 2,6-dichlorophenyl-substituted ligand 1a was found to be generally the most effective for a range of substrates, affording products from 83–94% enantiomeric excess. Although endo:exo diastereoselectivity for the oxo-substituted imides 2a–2d

  我们报道了酰亚胺衍生的亲二烯体2a - 2d和4b - 4d与环戊二烯的方形平面Cu（OTf）2-双（亚胺）配合物的Diels-Alder反应。人们发现，2,6-二氯苯基取代的配体1a通常对多种底物最有效，提供的对映体过量为83-94％。尽管对氧代取代的酰亚胺2a - 2d的内消旋非对映选择性很低，但噻唑烷-2-硫酮类似物4b - 4d可以显着改善，它提供了更强的亲二烯反应性和内消旋非对映选择性。
• Chiral Bis(oxazoline)copper(II) Complexes as Lewis Acid Catalysts for the Enantioselective Diels−Alder Reaction
  作者：David A. Evans、Scott J. Miller、Thomas Lectka、Peter von Matt

  DOI：10.1021/ja991190k

  日期：1999.8.1

  Bis(oxazoline)copper(II) complexes are highly enantioselective catalysts in Diels−Alder reactions involving bidentate dienophiles. Cationic [Cu((S,S)-t-Bu-box)]X2 complexes with different counterions have been used as catalysts, revealing a profound influence of the counterion on the rate and stereoselectivity of the catalyst. A square-planar catalyst−substrate complex is proposed to account for the

  双（恶唑啉）铜（II）配合物是涉及双齿亲二烯体的 Diels-Alder 反应中的高度对映选择性催化剂。具有不同抗衡离子的阳离子 [Cu((S,S)-t-Bu-box)]X2 配合物已被用作催化剂，揭示了抗衡离子对催化剂的速率和立体选择性的深远影响。提出了方形平面催化剂 - 底物复合物来解释观察到的高非对映选择性和对映选择性。已获得支持该模型的三个双（恶唑啉）-Cu（II）X 射线结构。使用手性亲二烯体进行的双立体分化实验提供的结果与所提出的方形平面过渡态组合完全一致。除了基于酰亚胺的底物，α、β-不饱和噻唑烷-2-硫酮作为一类具有增强反应性的新型亲二烯体被引入。进行动力学实验以量化产物抑制在反应过程中所起的作用。率和均衡...
• Enantioselective Friedel−Crafts Alkylations Catalyzed by Bis(oxazolinyl)pyridine−Scandium(III) Triflate Complexes
  作者：David A. Evans、Keith R. Fandrick、Hyun-Ji Song、Karl A. Scheidt、Risheng Xu

  DOI：10.1021/ja072976i

  日期：2007.8.1

  The enantioselective Friedel-Crafts addition of a variety of indoles catalyzed by bis(oxazolinyl)pyridine-scandium(III) triflate complexes (Sc(III)-pybox) was accomplished utilizing a series of beta-substituted alpha,beta-unsaturated phosphonates and alpha,beta-unsaturated 2-acyl imidazoles. The acyl phosphonate products were efficiently transformed into esters and amides, whereas the acyl imidazole adducts were converted to a broader spectrum of functionalities such as esters, amides, carboxylic acids, ketones, and aldehydes. The sense of stereoinduction and level of enantioselectivity were found to be functions of the size of the substrate employed, the substitution on the ligand, and the catalyst loading. Molecular modeling of the catalyst with the bound substrates was performed based on the crystal structures of the catalyst complexes and the sense of stereoinduction observed in the addition reaction. Nonlinear effects over a range of catalyst concentrations implicate a mononuclear complex as the active catalyst.