cis-2-(4-methylstyryl)thiophene | 50626-11-4

• 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: cis-2-(4-methylstyryl)thiophene
• 英文别名: (Z)-2-(4-methylstyryl)thiophene；2-[(Z)-2-(4-methylphenyl)ethenyl]thiophene
• CAS: 50626-11-4
• 化学式: C₁₃H₁₂S
• 分子量: 200.304
• InChiKey: BOEZUVGDVWVKRQ-HJWRWDBZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1-(4-methylbenzyl)-1H-benzo[d][1,2,3]triazole 在 sodium tetrahydroborate 、 正丁基锂 、 titanium(III) chloride 、 铜 、 锌 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 生成 cis-2-(4-methylstyryl)thiophene
  参考文献：
  名称：

  Benzotriazole-Mediated Stereoselective Olefination of Carboxylic Esters:  Transformation of α-Amino Acid Esters into Chiral Allylamines

  摘要：

  Diastereoselective trans-olefinations of carboxylic esters 3a-h have been accomplished using benzylic or allylic benzotriazole derivatives la-e to prepare alpha-(benzotriazol-1-yl) ketones 4a-i, for the subsequent reduction of 4a-i, and finally for low-valent titanium-effected dehydroxybenzotriazolylation.(1) N-Protected alpha-amino acid esters 9a-c and 15 thus give allylamines 13a-e and 19 with virtually full retention of chirality. Mechanistic aspects of the dehydroxybenzotriazolylation are discussed.

  DOI：

  10.1021/jo971546f

文献信息

• New Uncharged 2-Thienostilbene Oximes as Reactivators of Organophosphate-Inhibited Cholinesterases
  作者：Milena Mlakić、Tena Čadež、Danijela Barić、Ivana Puček、Ana Ratković、Željko Marinić、Kornelija Lasić、Zrinka Kovarik、Irena Škorić

  DOI：10.3390/ph14111147

  日期：——

  comprises an antimuscarinic drug and an oxime reactivator of the inhibited enzyme. Oximes in use have quaternary nitrogens, and therefore poorly cross the brain–blood barrier. In this work, we synthesized novel uncharged thienostilbene oximes by the Wittig reaction, converted to aldehydes by Vilsmeier formylation, and transformed to the corresponding uncharged oximes in very high yields. Eight trans,anti-

  作为神经毒剂和杀虫剂的有机磷 (OP) 对乙酰胆碱酯酶 (AChE) 和丁酰胆碱酯酶 (BChE) 的抑制会损害外周和中枢神经系统 (CNS) 中的正常胆碱能神经信号转导，从而导致胆碱能危象。治疗包括抗毒蕈碱药物和被抑制酶的肟再活化剂。使用中的肟含有季氮，因此很难穿过脑血屏障。在这项工作中，我们通过 Wittig 反应合成了新型不带电荷的噻吩并芪肟，通过 Vilsmeier 甲酰化转化为醛，并以非常高的产率转化为相应的不带电荷的肟。八反、反和反、同肟的异构体作为神经毒剂抑制的 AChE 和 BChE 的再活化剂进行了测试。四种衍生物在两小时内重新激活环沙林抑制的 BChE 高达 70%，对接研究证实了它们与环沙林抑制的 BChE 活性位点的有效相互作用。基于 AChE 和 BChE 对所有选定肟的中等结合亲和力，并在计算机上评估了 ADME 在亲脂性和 CNS 活性方面​​的特性，这些化合物呈现出一类新的肟，具有进一步开发
• Stereodivergent Zweifel Olefination and its Mechanistic Dichotomy
  作者：Samir Manna、Swagata Paul、Wang‐Yeuk Kong、Debasis Aich、Rupam Sahoo、Dean J. Tantillo、Santanu Panda

  DOI：10.1002/anie.202309136

  日期：2023.9.18

  Stereoselective Zweifel olefination using boronate complexes carrying two different reactive π‐systems was achieved to synthesize vinyl heteroarenes and conjugated 1,3‐dienes in good yield and up to 100 % stereoselectivity, which remains unexplored until now. Most importantly, we report the unprecedented formation of E vs. Z‐vinyl heteroarenes for different heteroarenes under identical conditions. Density functional theory (DFT) investigations unveil the mechanistic dichotomy between olefin and heteroarene activation followed by 1,2‐migration, leading to E or Z‐vinyl heteroarenes respectively. We also report a previously unknown reversal of stereoselectivity by using 2,3‐Dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) as an electrophile. The Zweifel olefination using a boronate complex that carries two different olefins was previously unexplored due to significant challenges associated with the site‐selective activation of olefins. We have solved this problem and reported the site‐selective activation of olefins for the stereoselective synthesis of 1,3‐dienes.

  摘要利用携带两种不同反应性 π-系统的硼酸盐配合物实现了全选择性 Zweifel 烯化反应，从而以良好的收率和高达 100 % 的立体选择性合成了乙烯基杂环戊烯和共轭 1,3 二烯，这一点迄今为止仍未得到探索。最重要的是，我们报告了在相同条件下不同杂环戊烯与 Z-乙烯基杂环戊烯前所未有的形成过程。密度泛函理论（DFT）研究揭示了烯烃和杂环戊烯活化后 1,2 迁移分别导致 E 或 Z 乙烯基杂环戊烯的机理二分法。我们还报告了通过使用 2,3-二氯-5,6-二氰基-1,4-苯醌（DDQ）作为亲电子体，实现了一种之前未知的立体选择性逆转。由于烯烃的位点选择性活化存在巨大挑战，使用携带两种不同烯烃的硼酸酯复合物进行 Zweifel 烯化反应的研究以前从未进行过。我们已经解决了这一问题，并报告了用于立体选择性合成 1,3 二烯的烯烃位点选择性活化。
• Benzotriazole-Mediated Stereoselective Olefination of Carboxylic Esters:  Transformation of α-Amino Acid Esters into Chiral Allylamines
  作者：Alan R. Katritzky、Dai Cheng、Jianqing Li

  DOI：10.1021/jo971546f

  日期：1998.5.1

  Diastereoselective trans-olefinations of carboxylic esters 3a-h have been accomplished using benzylic or allylic benzotriazole derivatives la-e to prepare alpha-(benzotriazol-1-yl) ketones 4a-i, for the subsequent reduction of 4a-i, and finally for low-valent titanium-effected dehydroxybenzotriazolylation.(1) N-Protected alpha-amino acid esters 9a-c and 15 thus give allylamines 13a-e and 19 with virtually full retention of chirality. Mechanistic aspects of the dehydroxybenzotriazolylation are discussed.