S-benzyl 2-phenylpropanethioate

• 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-benzyl 2-phenylpropanethioate
• 化学式: C₁₆H₁₆OS
• 分子量: 256.368
• InChiKey: QIHDKPSKBXEJBA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  18
• 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：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  S-benzyl 2-phenylpropanethioate 在 氘代甲醇 、 三乙胺 作用下， 以 氘代甲苯 为溶剂， 生成
  参考文献：
  名称：

  Dynamic Enzymatic Resolution of Thioesters

  摘要：

  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.

  DOI：

  10.1021/ja980445b
• 作为产物：
  描述：

  2-苯基丙酸 在 草酰氯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 S-benzyl 2-phenylpropanethioate
  参考文献：
  名称：

  Dynamic Enzymatic Resolution of Thioesters

  摘要：

  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.

  DOI：

  10.1021/ja980445b

文献信息

• Palladium‐Catalyzed Enantioselective Thiocarbonylation of Styrenes
  作者：Xihong Wang、Bing Wang、Xuemei Yin、Wangzhi Yu、Yang Liao、Jialin Ye、Min Wang、Lianrui Hu、Jian Liao

  DOI：10.1002/anie.201905905

  日期：2019.8.26

  A highly enantioselective thiocarbonylation of styrenes with CO and thiols has been achieved by Pd catalysis, providing highly enantioenriched thioesters in good to excellent yields. Key to the successful execution of this reaction is the use of a chiral sulfoxide-(P-dialkyl)-phosphine (SOP) ligands. This thiocarbonylation proceeds smoothly under mild reaction conditions (1 atm CO and 0 °C) and displays

  通过Pd催化，已实现了用CO和硫醇对苯乙烯进行高度对映选择性的硫羰基化反应，从而以良好或优异的收率提供了高度对映体富集的硫酯。该反应成功进行的关键是使用手性亚砜-（P-二烷基）-膦（SOP）配体。这种硫羰基化反应在温和的反应条件（1个大气压的CO和0°C）下平稳进行，并显示出较宽的底物范围。还证明了可以使用一氧化碳替代物进行这种转化，从而大大提高了反应进行的安全性。该方法的普遍性和实用性通过将其应用于硫酯产物的合成转化和含半胱氨酸的二肽的直接酰化而得以体现。研究了其主要机理并提出了合理的催化循环。
• 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。
• 一种通过烯烃插羰硫酯化合成硫酯类化合物 的方法
  申请人：中国科学院成都生物研究所

  公开号：CN110183366B

  公开（公告）日：2021-02-26

  本发明属于化工合成领域，具体涉及一种通过钯催化的烯烃插羰硫酯化合成手性或非手性硫酯类化合物的方法。具体的技术方案为：一种硫酯类化合物的合成方法，所述合成过程在通风环境中进行，将钯源、配体和溶剂混匀，搅拌30min，得到反应液；向所述反应液中加入添加剂、酸和抑制剂，混匀后，于‑20℃～25℃下搅拌；再依次加入硫醇、烯烃，在‑20℃～25℃下反应12～24h；反应结束后，通过分离纯化得到硫酯化合物。本发明提供了一种温和条件下通过烯烃插羰硫酯化的方法，该方法可用于对药物、氨基酸和多肽等的后修饰。
• One-Pot Synthesis of Alkyl Styryl Sulfides Free from Transition Metal/Ligand Catalyst and Thiols
  作者：Adrián A. Heredia、Alicia B. Peñéñory

  DOI：10.1002/ejoc.201201163

  日期：2013.2

  developed. This methodology involves the in situ generation of thiolate anions by nucleophilic substitution between potassium thioacetate and alkyl halides followed by fragmentation. Further reactions of these thiolate anions with substituted (E,Z)-β-styryl halides gave the corresponding sulfides with retention of stereochemistry in good to excellent yields. This procedure does not require a metal catalyst

  开发了一种新的苯乙烯基烷基硫化物一锅合成方案。该方法涉及通过硫代乙酸钾和烷基卤化物之间的亲核取代，然后进行碎裂，原位生成硫醇盐阴离子。这些硫醇盐阴离子与取代的 (E,Z)-β-苯乙烯基卤化物的进一步反应得到相应的硫化物，并以良好至极好的产率保留立体化学。该过程不需要金属催化剂，它在温和的条件下和短时间内进行，并且它没有恶臭和对空气敏感的烷基硫醇。
• 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