S-(tert-butyl) 2-oxo-2-phenylethanethioate | 959625-33-3

• 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-(tert-butyl) 2-oxo-2-phenylethanethioate
• 英文别名: S-tert-butyl 2-oxo-2-phenylethanethioate
• CAS: 959625-33-3
• 化学式: C₁₂H₁₄O₂S
• 分子量: 222.308
• InChiKey: CEDRYNWRXCIEJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  59.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  S-(tert-butyl) 2-oxo-2-phenylethanethioate 在 C₇₄H₇₄N₅O₂Si⁽¹⁺⁾*Br^(1-) 、 重水 、 四氯化钛 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 potassium hydroxide 作用下， 以 二氯甲烷 、 间二甲苯 、 甲苯 为溶剂， 反应 2.25h， 生成
  参考文献：
  名称：

  Phase-transfer catalysed asymmetric synthesis of α-chiral tetrasubstituted α-aminothioesters

  摘要：

  α-四取代-α-氨基硫酯通过手性相转移催化的Michael反应合成，产率高达97%，对映选择性高达81%。

  DOI：

  10.1039/d1ob00829c
• 作为产物：
  描述：

  DL-扁桃酸甲酯 在 氢氧化钾 、 草酰氯 、 氧气 、 三氯一氧化钒 三氯代氧化钒(V) 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 0.5h， 生成 S-(tert-butyl) 2-oxo-2-phenylethanethioate
  参考文献：
  名称：

  Asymmetric Aerobic Oxidation of α-Hydroxy Acid Derivatives by C₄-Symmetric, Vanadate-Centered, Tetrakisvanadyl(V) Clusters Derived from N-Salicylidene-α-aminocarboxylates

  摘要：

  A series of chiral vanadyl(V) methoxides bearing 3-t-butyl-5-substituted N-salicylene-L-valinate and L-t-leucinate as chiral auxiliaries has been prepared. In all cases except the 3,5-di-t-butyl analogue, they exist as monomers both in solution and in the single crystal state. In the case of the 3,5-di-t-butyl analogue, the architectural nature of the vanadyl(V) complex highly depends on the base used during the complex formation event. A pentanuclear C-4-symmetric complex was formed when potassium salts were employed instead of the corresponding sodium salts. A central vanadate(V) unit serves to grip four identical chiral monomeric vanadyl(V) units together, by which a potassium ion sits on top of the four flanking units through carbonyl coordinations and serves to hold the whole cluster by cooperation with the central vanadate(V) unit. In comparison with the corresponding monomeric vanadyl(V) methoxide complex, the cluster complex was utilized to facilitate the asymmetric aerobic oxidations of various racemic alpha-hydroxyesters, -amides, and -thioesters with excellent selectivity factors (k(rel) 40 to >500).

  DOI：

  10.1021/jo070575f

文献信息

• Non‐Bonding 1,4‐Sulphur‐Oxygen Interaction Governs the Reactivity of α‐Ketothioesters in Triphenylphosphine‐Catalyzed Cyclization with Acetylenedicarboxylates
  作者：Abhijit Bankura、Jayanta Saha、Rajib Maity、Indrajit Das

  DOI：10.1002/adsc.202001376

  日期：2021.2.16

  1,4‐interaction involving C−S σ* orbital on the sulphur atom and the lone pair of electrons in the electron‐donating oxygen atom. This is apparent from the X‐ray crystallographically determined internuclear distance between the sulphur and ketone (C=O) oxygen atoms (2.71–2.85 Å), which is significantly less than the sum of their van der Waals radii (3.25–3.30 Å). The substitution on the S atom is oriented

  α-酮硫酯经过三苯基膦（PPh 3）与乙二酮酸酯的催化环化反应平稳，而α-酮氧酸酯则需要更苛刻的条件和有限的底物范围。该反应可与各种α-酮硫代酯很好地结合，以中等至极好的收率提供高度官能化的α，β-不饱和γ-丁内酯。硫酯衍生物的较高反应性似乎是由于有利的分子内非键合静电1,4-相互作用，涉及硫原子上的Cσσ*轨道和给电子氧原子中的孤对电子。从X射线晶体学确定的硫和酮（C = O）氧原子之间的核间距离（2.71-2.85Å）可以明显看出，该距离明显小于其范德华半径的总和（3.25-3.30Å） 。S原子上的取代沿直径方向远离酮O原子，以使它们之间的相互作用最大化。γ-丁内酯产品中S与呋喃O原子（2.70Å）之间的1,4-S⋅⋅⋅O接触也可以看到这种趋势。
• ESR studies on carboxylic esters. Part 13—electron spin resonance spectroscopy and molecular orbital calculations on the radical anions of 2-oxo-carbothioate and 2-oxo-carbodithioate esters
  作者：J. Gassmann、H. Günther、K. Osternack、A. Sawluk、K. Thimm、J. Voss

  DOI：10.1002/mrc.1260321011

  日期：1994.10

  Radical anions of alkyl α‐oxocarbothioates and α‐oxocarbodithioates are generated by in situ electroreduction. Their spin density distribution and configuration are discussed in terms of the ESR spectra and semi‐empirical (McLachlan‐type and AM1) MO calculations.

  烷基α-氧代碳硫酸酯和α-氧代碳二硫代的自由基阴离子是通过原位电还原产生的。根据 ESR 谱和半经验（McLachlan 型和 AM1）MO 计算讨论了它们的自旋密度分布和配置。
• Asymmetric Synthesis of Carboxylic Acid Derivatives Having an All-Carbon α-Quaternary Center through Cu-Catalyzed 1,4-Addition of Dialkylzinc Reagents to 2-Aryl Acetate Derivatives
  作者：Ashraf Wilsily、Eric Fillion

  DOI：10.1021/ol800923q

  日期：2008.7.3

  The asymmetric synthesis of carboxylic acid derivatives having an all-carbon alpha-quaternary center has been achieved via copper-catalyzed 1,4-addition of dialkylzinc reagents to aryl acetate derivatives in the presence of phosphoramidite ligand. High isolated yields and enantioselectivities were obtained. It was demonstrated that the Meldrum's acid and ester moieties present on the all-carbon quaternary

  在亚磷酰胺配体的存在下，通过铜催化的将二烷基锌试剂与乙酸芳基酯衍生物进行铜催化的1,4-加成反应，可以实现具有全碳α-季中心的羧酸衍生物的不对称合成。获得了高分离产率和对映选择性。事实证明，存在于全碳四元中心上的Meldrum酸和酯部分可以进行多种后续转化，从而可以方便地制备琥珀酰亚胺，琥珀酸酯和琥珀酸，γ-丁内酯和β-氨基酸衍生品。
• Access to Multifunctionalized Tetrasubstituted Carbon Centers Bearing up to Three Different Heteroatoms via Tandem Geminal Chlorofluorination of 1,2-Dicarbonyl Compounds
  作者：Ha Eun Kim、Mugeon Song、Sunjoo Hwang、Won-jin Chung

  DOI：10.1021/acs.orglett.3c03527

  日期：2023.12.15

  of each function. However, despite increasing interest in the controllable installation of heteroatoms, it has been extremely challenging to construct carbon centers having three different heteroatoms in a synthetically useful manner. In this work, our group’s tandem geminal chlorofluorination (Cl, F) strategy was applied to rationally designed heteroatom-bearing 1,2-dicarbonyl substrates, including

  将非碳杂原子掺入有机分子通常会赋予其特征性且通常有价值的功能。不同杂原子的共存可以通过协同效应进一步拓宽它们的效用，这甚至可能导致发现以前无法获得的特性，而不仅仅是每个功能的简单积累。然而，尽管人们对杂原子的可控安装越来越感兴趣，但以合成有用的方式构建具有三种不同杂原子的碳中心仍然极具挑战性。在这项工作中，我们小组的串联孪生氯氟化（Cl，F）策略应用于合理设计的带有杂原子的1,2-二羰基底物，包括α-酮硫酯（S）、α-酮N-酰基吲哚（N）和α-酮酰基硅烷（Si），导致具有优异位点选择性的双或三杂官能化四取代碳中心的实际生产。
• Asymmetric Aerobic Oxidation of α-Hydroxy Acid Derivatives by <i>C</i>₄-Symmetric, Vanadate-Centered, Tetrakisvanadyl(V) Clusters Derived from <i>N</i>-Salicylidene-α-aminocarboxylates
  作者：Chien-Tien Chen、Sampada Bettigeri、Shiue-Shien Weng、Vijay D. Pawar、Ya-Hui Lin、Cheng-Yuan Liu、Way-Zen Lee

  DOI：10.1021/jo070575f

  日期：2007.10.1

  A series of chiral vanadyl(V) methoxides bearing 3-t-butyl-5-substituted N-salicylene-L-valinate and L-t-leucinate as chiral auxiliaries has been prepared. In all cases except the 3,5-di-t-butyl analogue, they exist as monomers both in solution and in the single crystal state. In the case of the 3,5-di-t-butyl analogue, the architectural nature of the vanadyl(V) complex highly depends on the base used during the complex formation event. A pentanuclear C-4-symmetric complex was formed when potassium salts were employed instead of the corresponding sodium salts. A central vanadate(V) unit serves to grip four identical chiral monomeric vanadyl(V) units together, by which a potassium ion sits on top of the four flanking units through carbonyl coordinations and serves to hold the whole cluster by cooperation with the central vanadate(V) unit. In comparison with the corresponding monomeric vanadyl(V) methoxide complex, the cluster complex was utilized to facilitate the asymmetric aerobic oxidations of various racemic alpha-hydroxyesters, -amides, and -thioesters with excellent selectivity factors (k(rel) 40 to >500).