methyl 2-(thiophene-2-carbonyl)pent-4-enedithioate | 1613031-29-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-(thiophene-2-carbonyl)pent-4-enedithioate
• 英文别名: Methyl 2-(thiophene-2-carbonyl)pent-4-enedithioate
• CAS: 1613031-29-0
• 化学式: C₁₁H₁₂OS₃
• 分子量: 256.414
• InChiKey: XNSAUMKJIKETAA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  103
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 2-(thiophene-2-carbonyl)pent-4-enedithioate 在 bis-triphenylphosphine-palladium(II) chloride 、 potassium carbonate 、 三苯基膦 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以86%的产率得到2-(methylthio)-3-(2-thienoyl)-4H-thiopyran
  参考文献：
  名称：

  Regioselective Synthesis of Dihydrothiophene and Thiopyran Frameworks via Catalyst-Controlled Intramolecular C_γ/C_δ–S Fusion of α-Allyl-β′-oxodithioesters

  摘要：

  A highly efficient and atom-economic dual reaction manifold has been developed to synthesize 4H-thiopyran and 4,5-dihydrothiophene frameworks via regioselective intramolecular C-S fusion of alpha-allyl-beta'-oxodithioesters. The ring size of the sulfur-heterocycles has been efficiently tuned by the use of two different catalytic systems. Palladium activates the Cd-H of the allyl termini and facilitates the intramolecular C delta-S coupling to furnish six-membered thiopyran skeletons exclusively. Conversely, the allylic double bond of the same substrate has been activated by to promote the C delta-S cyclization leading to the formation of a five-membered dihydrothiophene nucleus.

  DOI：

  10.1021/ol502850h
• 作为产物：
  描述：

  methyl 3-hydroxy-3-(thiophen-2-yl)prop-2-enedithioate 、 3-溴丙烯 在 indium 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以82%的产率得到methyl 2-(thiophene-2-carbonyl)pent-4-enedithioate
  参考文献：
  名称：

  铟（0）介导的 C sp 3-S/O 交叉偶联方法实现 α-烯醇酯/二硫酯的区域选择性烷基化：机理洞察

  摘要：

  我们已经报道了一种铟（0）介导的 C sp 3-S/O 交叉偶联方法，该方法导致 α-烯醇乙酸酯/二硫代乙酸酯系统的高度区域选择性烷基化。这种杂交叉偶联反应不需要额外的助催化剂或促进剂，原位生成的有机铟物质通过充当 α-烯醇乙酸酯/二硫代乙酸酯底物的偶联伙伴来促进反应。C-、S- 或 O-烷基化的出色选择性完全取决于 α-烯醇乙酸酯/二硫代乙酸酯体系的亲核行为。这些结果得到了底物和产物的相对电子能量的 DFT 计算以及相应转换的激活势垒的进一步支持。

  DOI：

  10.1002/ejoc.201301788

文献信息

• In/I2 mediated functional group transformation: a direct approach toward the selective conversion of dithioester to ester
  作者：Sushobhan Chowdhury、Suvajit Koley、Tanmoy Chanda、Maya Shankar Singh

  DOI：10.1016/j.tetlet.2015.08.035

  日期：2015.10

  A facile, direct approach for the selective conversion of dithioester to ester functional group has been developed. In/I2 in methanol efficiently promotes the interesting functional group transformation at room temperature. Applying the newly developed mild conditions, a series of α-allyl-β′-oxodithioesters have been converted to the corresponding α-allyl-β′-oxoesters in moderate to good yields. Interestingly

  已经开发了一种简便，直接的方法，用于将二硫酯选择性转化为酯官能团。甲醇中的In / I 2有效地促进了室温下有趣的官能团转化。应用新近开发的温和条件，一系列α-烯丙基-β'-氧代二硫代酯已以中等至良好的产率转化为相应的α-烯丙基-β'-氧代酯。有趣的是，在转化过程中，起始α-烯丙基-β'-氧代二硫代酯的二硫酯基团被选择性地转化为相应的甲酯，而该部分内的其他官能团不受影响。因此，在合成转化过程中不需要繁琐的保护-去保护。
• Regio- and Chemoselective Access to Dihydrothiophenes and Thiophenes via Halogenation/Intramolecular C(sp²)–H Thienation of α-Allyl Dithioesters at Room Temperature
  作者：Gaurav Shukla、Keshav Raghuvanshi、Maya Shankar Singh

  DOI：10.1021/acs.joc.2c01617

  日期：2022.11.4

  (NBS/NIS) to an allylic double bond, followed by intramolecular regio- and chemoselective S-cyclization. This protocol avoids potential toxicity and tedious work-up conditions, and features easy synthesis from readily available starting materials under catalyst-free conditions. Furthermore, 4,5-dihydrothiophenes were aromatized to thiophenes by treatment with KOH in DMF at room temperature. A probable

  已经实现了一种操作简单、实用且高效的级联方法，使用 α-烯丙基二硫酯和 NBS/NIS 来获得一系列二氢噻吩和包含不同电子和空间性质的不同官能团的噻吩，在室温下在开放条件下以良好至优异的产率空气。该反应通过卤素源 (NBS/NIS) 与烯丙基双键的亲电加成，然后是分子内区域选择性和化学选择性S-环化。该协议避免了潜在的毒性和繁琐的后处理条件，并具有在无催化剂条件下从现成的起始材料轻松合成的特点。此外，通过在 DMF 中在室温下用 KOH 处理，将 4,5-二氢噻吩芳构化为噻吩。已经提出了从α-烯丙基二硫酯形成二氢噻吩和噻吩的可能机制。值得注意的是，与合成 4,5-二氢噻吩和噻吩的竞争工艺相比，大规模实验和产物转化表明该反应的潜在效用。
• Indium(0)-Mediated C sp 3-S/O Cross-Coupling Approach Towards the Regioselective Alkylation of α-Enolic Esters/Dithioesters: A Mechanistic Insight
  作者：Sushobhan Chowdhury、Tanmoy Chanda、Ashutosh Gupta、Suvajit Koley、B. Janaki Ramulu、Raymond C. F. Jones、Maya Shankar Singh

  DOI：10.1002/ejoc.201301788

  日期：2014.5

  We have reported an indium(0)-mediated C sp 3–S/O cross-coupling approach that leads to the highly regioselective alkylation of α-enolic acetate/dithioacetate systems. This hetero cross-coupling reaction does not require additional co-catalyst or promoter, and the in situ generated organoindium species promotes the reaction by acting as the coupling partner of the α-enolic acetate/dithioacetate substrates

  我们已经报道了一种铟（0）介导的 C sp 3-S/O 交叉偶联方法，该方法导致 α-烯醇乙酸酯/二硫代乙酸酯系统的高度区域选择性烷基化。这种杂交叉偶联反应不需要额外的助催化剂或促进剂，原位生成的有机铟物质通过充当 α-烯醇乙酸酯/二硫代乙酸酯底物的偶联伙伴来促进反应。C-、S- 或 O-烷基化的出色选择性完全取决于 α-烯醇乙酸酯/二硫代乙酸酯体系的亲核行为。这些结果得到了底物和产物的相对电子能量的 DFT 计算以及相应转换的激活势垒的进一步支持。
• Regioselective Synthesis of Dihydrothiophene and Thiopyran Frameworks via Catalyst-Controlled Intramolecular C_γ/C_δ–S Fusion of α-Allyl-β′-oxodithioesters
  作者：Sushobhan Chowdhury、Tanmoy Chanda、Suvajit Koley、Namrata Anand、Maya Shankar Singh

  DOI：10.1021/ol502850h

  日期：2014.11.7

  A highly efficient and atom-economic dual reaction manifold has been developed to synthesize 4H-thiopyran and 4,5-dihydrothiophene frameworks via regioselective intramolecular C-S fusion of alpha-allyl-beta'-oxodithioesters. The ring size of the sulfur-heterocycles has been efficiently tuned by the use of two different catalytic systems. Palladium activates the Cd-H of the allyl termini and facilitates the intramolecular C delta-S coupling to furnish six-membered thiopyran skeletons exclusively. Conversely, the allylic double bond of the same substrate has been activated by to promote the C delta-S cyclization leading to the formation of a five-membered dihydrothiophene nucleus.