S-ethyl 2-phenylpropanethioate | 169139-76-8

• 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: S-ethyl 2-phenylpropanethioate
• CAS: 169139-76-8
• 化学式: C₁₁H₁₄OS
• 分子量: 194.298
• InChiKey: JWUWDWSKALXSHG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.07
• 重原子数：
  13.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  S-ethyl 2-phenylpropanethioate 在 重水 、 4-羟乙基哌嗪乙磺酸 作用下， 反应 48.0h， 生成 C₁₁H₁₃⁽²⁾HOS
  参考文献：
  名称：

  工程化丙二酸丙二酸脱羧酶的混杂消旋酶活性

  摘要：

  支气管败血波氏杆菌中的芳基丙二酸脱羧酶（AMDase）G74C变体对profens具有独特的消旋作用。通过蛋白质工程，基于脱羧反应的活性降低和消旋活性的两倍提高，获得了向混杂消旋化20倍的变体G74C / V43A。该突变体显示出扩大的底物范围，对酮洛芬的反应速率提高了30倍。分子动力学模拟和消旋酶的底物特征表明，底物结构的空间和极性效应在催化方面比单纯的动力学α-质子酸度起着更大的作用。β，γ-不饱和羧酸的转化不会导致重排形成其α，β异构体的观察结果表明，这是一个协调的机制，而不是逐步的机制。有趣的是，

  DOI：

  10.1002/chem.201001924
• 作为产物：
  描述：

  (E)-(1-phenylethyl)(ethylthio)sulfine 以 四氯化碳 为溶剂， 反应 2.5h， 以72%的产率得到S-ethyl 2-phenylpropanethioate
  参考文献：
  名称：

  通过二硫代酯的氧化合成手性亚砜

  摘要：

  sulfines的合成（硫酮氧化物）（2，10和17）从三个手性二硫代酯（衍生1,8和16）的轴承在α碳原子上的氢进行说明。在C-α（2）处带有酰胺基的硫磺不会消旋，并且长期稳定。当亚砜（10）中的C-α带有乙酰氧基时，光学活性在两个月的时间内保持不变。在更长的储存时间之后，发生重排成二硫代过氧酯12和S-甲酯11的混合物。在C-α处有烷基的亚砜17经历快速消旋并缓慢重排为S-乙酯14，二硫代过氧酯18和S-乙烯基硫代亚磺酸盐19的混合物。

  DOI：

  10.1002/recl.19951140304

文献信息

• Nickel-Catalyzed Coupling of Arylzinc Halides with Thioesters
  作者：Paul H. Gehrtz、Prasad Kathe、Ivana Fleischer

  DOI：10.1002/chem.201801887

  日期：2018.6.21

  The Pd‐catalyzed Fukuyama reaction of thioesters with organozinc reagents is a mild, functional‐group‐tolerant method for acylation chemistry. Its Ni‐catalyzed variant might be a sustainable alternative to expensive catalytic Pd sources. We investigated the reaction of S‐ethyl thioesters with aryl zinc halides with hetero‐ and homotopic Ni precatalysts and several ligands. The results show that both

  Pd催化的硫酯与有机锌试剂的Fukuyama反应是温和的，对官能团具有耐受性的酰化化学方法。其Ni催化的变体可能是昂贵的Pd催化源的可持续替代方案。我们研究了S-乙基硫代酯与芳基卤化锌与杂和同位Ni预催化剂和几种配体的反应。结果表明，同位和异位物种均可促进催化作用。确定了使用可操作均匀定义的Ni配合物的底物范围。假定酰基为短寿命的中间体。
• A Mild Method for Access to α‐Substituted Dithiomalonates through C‐Thiocarbonylation of Thioester: Synthesis of Mesoionic Insecticides
  作者：Xinyue Yang、Yanrong Ma、Huiming Di、Xiaochen Wang、Hui Jin、Do Hyun Ryu、Lixin Zhang

  DOI：10.1002/adsc.202100369

  日期：2021.7

  An efficient method for targeting a variety of symmetrical and asymmetrical α-substituted dithiomalonates (DTMs) is described, utilizing 1H-imidazole-1-carbothioates as reactive acylating agents and MgBr2⋅OEt2/DBU or LiHMDS for soft or hard enolization conditions of thioesters, respectively. The utility of this methodology was demonstrated through the synthesis of the pyridopyrimidine mesoionic insecticides:

  描述了一种针对各种对称和非对称 α-取代二硫代丙二酸酯 (DTM) 的有效方法，利用 1 H -咪唑-1-碳硫代酸酯作为活性酰化剂，将 MgBr 2 ⋅OEt 2 /DBU 或 LiHMDS 用于软或硬烯醇化条件分别为硫酯。这种方法的实用性通过吡啶并嘧啶中离子杀虫剂的合成得到了证明：三氟嘧啶和双氯灭活。
• Regioselective Thiocarbonylation of Vinyl Arenes
  作者：Vera Hirschbeck、Paul H. Gehrtz、Ivana Fleischer

  DOI：10.1021/jacs.6b11020

  日期：2016.12.28

  A palladium-catalyzed thiocarbonylation of styrene derivatives is reported for the first time. The combination of thiols as nucleophiles and a bidentate ligand ensures a unique reaction outcome with high regioselectivity toward the more valuable branched isomer and new reactivity. The ambient reaction conditions (temperature, catalyst loading) and the use of a CO surrogate render this transformation

  首次报道了钯催化的苯乙烯衍生物的硫代羰基化。作为亲核试剂的硫醇和双齿配体的组合确保了独特的反应结果，对更有价值的支链异构体和新的反应性具有高区域选择性。环境反应条件（温度、催化剂负载）和 CO 替代物的使用使这种转化成为从可用原料合成硫酯的有用方法。该系统可以容忍芳烃和硫醇取代基上的各种官能团。值得注意的是，具有挑战性的邻位取代苯乙烯以前所未有的高区域选择性转化。
• Palladium-Catalyzed Thiocarbonylation of Alkenes toward Linear Thioesters
  作者：Han-Jun Ai、Fengqian Zhao、Hui-Qing Geng、Xiao-Feng Wu

  DOI：10.1021/acscatal.1c00414

  日期：2021.3.19
• Dynamic Enzymatic Resolution of Thioesters
  作者：Pil-Je Um、Dale G. Drueckhammer

  DOI：10.1021/ja980445b

  日期：1998.6.1

  A detailed investigation of several issues related to the enzymatic resolution of thioesters under conditions of continuous racemization of substrate was conducted. The kinetic acidity of the alpha-protons of a series of alpha-substituted propionate thioesters was studied. It was found that the rate of alpha-proton exchange could be enhanced as much as 20-fold by variation of the thiol moiety, increasing the range of compounds to which enzymatic dynamic resolution may be applied. The relative rates of hydrolysis of ethyl butyrate and ethyl thiobutyrate by several enzymes commonly used in enzymatic resolution were determined. All of the enzymes studied exhibited similar rates of thioester and oxoester hydrolysis except for the esterase from pig liver, which showed very low activity in thioester hydrolysis. Dynamic resolution of the propargyl and trifluoroethyl thioesters of alpha-phenylpropionate was conducted using subtilisin Carlsberg as a catalyst. These examples demonstrated that enzymatic dynamic resolution can be applied even when the rate of alpha-proton exchange and the enantioselectivity of the enzyme are fairly low. A dynamic enzymatic transesterification procedure was demonstrated in the resolution of the trifluoroethyl thioester of alpha-(2,4-dichlorophenoxy)propionate, and product was obtained in 93% ee. This work helps expand and define the scope of enzymatic dynamic resolution of thioesters.