methyl 2-benzoyl-4-methylpent-4-enedithioate | 1613031-26-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-benzoyl-4-methylpent-4-enedithioate
• 英文别名: Methyl 2-benzoyl-4-methylpent-4-enedithioate
• CAS: 1613031-26-7
• 化学式: C₁₄H₁₆OS₂
• 分子量: 264.412
• InChiKey: MDZOKUAPLWPTGD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  74.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-benzoyl-4-methylpent-4-enedithioate 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 以67%的产率得到3-benzoyl-5,5-dimethyl-2-(methylthio)-4,5-dihydrothiophene
  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-phenylprop-2-enedithioate 、 3-氯-2-甲基丙烯 在 indium 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以83%的产率得到methyl 2-benzoyl-4-methylpent-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

• 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.