methyl 2-(phenylthio)-2-(p-tolyl)acetate | 1644247-69-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: methyl 2-(phenylthio)-2-(p-tolyl)acetate
• 英文别名: Methyl 2-(4-methylphenyl)-2-phenylsulfanylacetate
• CAS: 1644247-69-7
• 化学式: C₁₆H₁₆O₂S
• 分子量: 272.368
• InChiKey: UORJDDJVFLYODZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-(phenylthio)-2-(p-tolyl)acetate 在 copper diacetate 作用下， 以 溶剂黄146 为溶剂， 反应 48.0h， 以80%的产率得到methyl 4-methylphenylglyoxylate
  参考文献：
  名称：

  铜催化的α-硫代芳基/杂芳基乙酸酯的Pummerer型反应：芳基/杂芳基α-酮基酯的合成

  摘要：

  首次描述了铜催化的α-硫代芳基/杂芳基乙酸酯的Pummerer型反应。这种转变代表了合成α-酮酯的新途径，这是药物和有机合成的重要中间体。该反应通过原位产生的硫鎓离子进行而进行，该硫鎓离子经过水解以合成上可行的产率（最高达82％）提供α-酮酯。

  DOI：

  10.1016/j.tetlet.2017.03.069
• 作为产物：
  描述：

  对甲苯基乙酸甲酯 在 对甲苯磺酰叠氮 、 tetrakis(actonitrile)copper(I) hexafluorophosphate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成 methyl 2-(phenylthio)-2-(p-tolyl)acetate
  参考文献：
  名称：

  铜催化α-重氮酸酯和α-重氮酮类化合物向Si–H和S–H键插入类固醇

  摘要：

  开发了一种有效的铜催化的α-重氮羰基化合物向Si-H和S-H键插入类胡萝卜素的插入反应。使用5 mol％的简单铜（I）盐作为催化剂，可以从α-重氮酸酯中以高收率（高达98％）获得各种α-甲硅烷基酯和α-硫代酯。使用0.05 mol％的相同催化剂，α-二氮酮会以低到良好的收率（最高70％）生成α-甲硅烷基酮。

  DOI：

  10.1021/acs.joc.6b02998

文献信息

• α-Thiocarbonyl synthesis<i>via</i>the Fe^II-catalyzed insertion reaction of α-diazocarbonyls into S–H bonds
  作者：Hoda Keipour、Angela Jalba、Nour Tanbouza、Virginie Carreras、Thierry Ollevier

  DOI：10.1039/c9ob00261h

  日期：——

  Fe(OTf)2 was used to catalyze the insertion reaction of α-diazocarbonyls into S–H bonds at 40 °C. A wide range of α-thioesters were obtained in yields up to 96% within 24–48 h from their corresponding α-diazoesters. A variety of thiols were used for the unprecedented insertion reaction with an α-diazoketone, leading to yields up to 85% of α-thioketones.

  Fe（OTf）2用于在40°C催化α-重氮羰基插入S–H键的插入反应。在24-48小时内，从其相应的α-重氮酯类中获得了范围广泛的α-硫酯类，收率高达96％。各种硫醇用于与α-二氮酮的前所未有的插入反应，从而导致高达85％的α-硫酮生成。
• Urea-Induced Acid Amplification: A New Approach for Metal-Free Insertion Chemistry
  作者：Erica D. Couch、Tyler J. Auvil、Anita E. Mattson

  DOI：10.1002/chem.201403283

  日期：2014.7.1

  α‐aryldiazoacetates in high yield. This methodology was found to be generally applicable to a broad substrate scope and presents a conceptually new approach for organocatalytic diazo insertion reactions. Mechanistic investigations suggest that the reaction pathway involves a urea‐induced protonation of the α‐aryldiazoester.

  事实证明，增强二氟硼酸脲的催化活性对于提高酸度α-芳基重氮乙酸酯的无金属OH和SH插入反应而言是必不可少的。发现该方法通常适用于广泛的底物范围，并且提出了用于有机催化重氮插入反应的概念上新的方法。机理研究表明，该反应途径涉及尿素诱导的α-芳基重氮酯的质子化。
• Straightforward access to α-carbonyloxy esters and β-keto thioethers from aryldiazoacetates
  作者：Naveen Kumar、Ajay Kant Gola、Satyendra Kumar Pandey

  DOI：10.1039/d3ob02104a

  日期：——

  A metal- and additive-free approach has been described for synthesizing α-carbonyloxy esters and β-keto thioethers from readily available aryldiazoacetates with carboxylic acids and thiol derivatives, respectively. α-Carbonyloxy esters and β-keto thioether derivatives were synthesized in good to high yields from aryldiazoacetates, carboxylic acids, and thiol derivatives decorated with various functional

  已经描述了一种无金属和无添加剂的方法，用于从容易获得的芳基重氮乙酸酯分别与羧酸和硫醇衍生物合成α-羰氧基酯和β-酮硫醚。由芳基重氮乙酸酯、羧酸和装饰有各种官能团的硫醇衍生物以良好到高的产率合成了 α-羰氧基酯和 β-酮硫醚衍生物。最后，通过其在克级反应和一些生物活性分子的合成中的应用证明了新方法的潜力。
• Scope and Mechanism of Iridium Porphyrin-Catalyzed S–H Insertion Reactions between Thiols and Diazo Esters
  作者：Taiwo O. Dairo、L. Keith Woo

  DOI：10.1021/acs.organomet.6b00947

  日期：2017.2.27

  The insertion of carbenes derived from ethyl diazoacetate (EDA), methyl diazoacetate (MDA), methyl phenyldiazoacetate (MPDA), and methyl (p-tolyl)diazoacetate (MTDA) into the S-H bonds of aromatic and aliphatic thiols was catalyzed by (5,10,15,20-tetratolylporphyrinato)methyliridium (III), Ir(TTP)CH3, at ambient temperatures. Yields of the resulting thioether products were as high as 97% for aromatic thiols, with catalyst loadings as low as 0.07 mol %. Thiol binding to Ir(TTP)CH3 was measured at 23 degrees C by titration studies,, providing equilibrium constants, K-b, ranging from 4.25 X 10(2) to 1.69 X 105 and increasing in the order p-nitrobenzenethiol < p-chlorobenzenethiol < benzenethiol < p-methylbenzenethiol < p-methoxybenzenethiol < benzyl mercaptan. Hammett plots were generated from the relative rates of S-H insertion, using different para-substituted benzenethiols in substrate competition experiments. In the presence of MIA and MTDA, the Hammett plots had slopes of -0.12 +/- 0.01 and -0.78 +/- 0.11, respectively. The Hammett data and kinetic studies are consistent with a mechanism that involves a rate-limiting nudeophilic attack of thiols on an iridium-carbene species, where the major species present in the reaction solution is an inactive, hexacoordinate Ir-thiol complex.