1,1-二甲基-3-(1H-1,2,4-三唑-5-基)硫代脲 | 124709-71-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 苯丙酸
• 中文名称: 1,1-二甲基-3-(1H-1,2,4-三唑-5-基)硫代脲
• 英文名称: R-(-)-2-(4'-methylphenyl)-propanoic acid
• 英文别名: (R)-2-(4-methylphenyl)propanoic acid；(R)-2-(4-methylphenyl)propionic acid；2-(4-methylphenyl)propanoic acid；(R)-2-(4-tolyl)propionic acid；(R)-2-(p-tolyl)propanoic acid；2-(p-tolyl)propanoic acid；(2R)-2-(4-methylphenyl)propanoic acid
• CAS: 124709-71-3
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: KDYOFXPLHVSIHS-MRVPVSSYSA-N

物化性质

• 沸点：
  278.0±9.0 °C(Predicted)
• 密度：
  1.091±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,1-二甲基-3-(1H-1,2,4-三唑-5-基)硫代脲 在 dimethyl sulfide borane 作用下， 以 乙醚 为溶剂， 以88%的产率得到(R)-2-p-tolylpropan-1-ol
  参考文献：
  名称：

  Catalytic Asymmetric Hydrocarboxylation and Hydrohydroxymethylation. A Two-Step Approach to the Enantioselective Functionalization of Vinylarenes

  摘要：

  A method for the catalytic asymmetric hydrocarboxylation and hydrohydroxymethylation of vinylarenes is reported. By separating the step in which asymmetry is installed from the one where carbon-carbon bond formation takes place, a highly enantioselective and regioselective synthesis of Ibuprofen and its analogs is achieved. Stereochemistry is installed via an enantioselective hydroboration reaction, catalyzed by cationic rhodium BINAP complexes, and the homologation is carried out with halomethyllithium reagents. If CH2Cl2/n-BuLi is used as the homologating reagent, carboxylic acids are produced after oxidation. On the other hand, if CH2ClBr is used in combination with n-BuLi, the corresponding primary alcohol is produced. This latter transformation represents a previously unknown asymmetric hydrohydroxymethylation reaction. In both cases, complete retention of stereochemistry is observed, yielding products in up to 97% ee. Superior results are obtained if the initially formed catecholate is converted into a pinacolate prior to homologation.

  DOI：

  10.1021/jo9914216
• 作为产物：
  描述：

  2-(p-methylphenyl)-1,3-propanediol 在 4-二甲氨基吡啶 sodium hydroxide 、 sodium tetrahydroborate 、 phosphate buffer 、 Jones'reagent 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 二甲基亚砜 、 丙酮 为溶剂， 反应 11.0h， 生成 1,1-二甲基-3-(1H-1,2,4-三唑-5-基)硫代脲
  参考文献：
  名称：

  Enzyme catalyzed monohydrolysis of 2-aryl-1 3-propanediol diacetates. A study of structural effects of the aryl moiety on the enantioselectivity

  摘要：

  DOI：

  10.1016/s0040-4020(01)87892-3

文献信息

• Biocatalytic Parallel Interconnected Dynamic Asymmetric Disproportionation of α‐Substituted Aldehydes: Atom‐Efficient Access to Enantiopure (<i>S</i>)‐Profens and Profenols
  作者：Erika Tassano、Kurt Faber、Mélanie Hall

  DOI：10.1002/adsc.201800541

  日期：2018.7.16

  disproportionation of aldehydes catalyzed by horse liver alcohol dehydrogenase (HLADH) was assessed in detail on a series of racemic 2‐arylpropanals. Statistical optimization by means of design of experiments (DoE) allowed the identification of critical interdependencies between several reaction parameters and revealed a specific experimental window for reaching an ′optimal compromise′ in the reaction outcome.

  对一系列外消旋 2-芳基丙醛，详细评估了马肝醇脱氢酶 (HLADH) 催化的醛的生物催化不对称歧化反应。通过实验设计 (DoE) 进行统计优化，可以识别多个反应参数之间的关键相互依赖性，并揭示了在反应结果中达到“最佳折衷”的特定实验窗口。该生物催化系统可应用于各种2-芳基丙醛，并在并行互连动态不对称转化（PIDAT）后以氧化还原中性方式获得对映体富集的（ S ）-洛芬和洛芬醇。该反应可以在环境条件下在水性缓冲液中进行，不依赖牺牲辅助底物，并且仅需要催化量的辅助因子和单一酶。高原子效率的例子是在〜0.013当量存在下， 75 mM的外消旋-2-苯基丙醛与0.03 mol%的HLADH的转化。氧化烟酰胺腺嘌呤二核苷酸 (NAD + )，在 96% ee中产生 28.1 mM ( S )-2-苯基丙醇，在 89% ee中产生 26.5 mM ( S )-2-苯基丙酸，总转化率为 73%。100 mg
• Total synthesis of wikstrol A and wikstrol B
  作者：Kui Lu、Ming Li、Yuna Huang、Yuanyuan Sun、Zhi Gong、Qijun Wei、Xia Zhao、Yongmin Zhang、Peng Yu

  DOI：10.1039/c9ob01219b

  日期：——

  reaction, Sharpless asymmetric dihydroxylation, regioselective iodination, Sonogashira coupling, and rhodium-catalyzed oxidative coupling as key steps. The structure of the key intermediate for wikstrol A was confirmed via its derivative by single-crystal X-ray analysis.

  wikstrol A和wikstrol B的第一个全合成是通过采用醛醇缩合反应，Sharpless不对称二羟基化，区域选择性碘化，Sonogashira偶联和铑催化的氧化偶联来实现的。wikstrol A的关键中间体的结构通过单晶X射线分析通过​​其衍生物确认。
• Enantioselective Synthesis of Chiral Carboxylic Acids from Alkynes and Formic Acid by Nickel‐Catalyzed Cascade Reactions: Facile Synthesis of Profens
  作者：Peng Yang、Yaxin Sun、Kaiyue Fu、Li Zhang、Guang Yang、Jieyu Yue、Yu Ma、Jianrong Steve Zhou、Bo Tang

  DOI：10.1002/anie.202111778

  日期：2022.1.3

  A simple nickel catalyst converts terminal alkynes and formic acid to α-chiral carboxylic acids in high enantioselectivity. The reaction proceeds via the hydrocarboxylation of alkynes and enantioselective transfer hydrogenation of acrylic acids.

  一种简单的镍催化剂以高对映选择性将末端炔烃和甲酸转化为 α-手性羧酸。该反应通过炔烃的加氢羧化和丙烯酸的对映选择性转移氢化进行。
• KetoABNO/NO_<i>x</i> Cocatalytic Aerobic Oxidation of Aldehydes to Carboxylic Acids and Access to α-Chiral Carboxylic Acids via Sequential Asymmetric Hydroformylation/Oxidation
  作者：Kelsey C. Miles、M. Leigh Abrams、Clark R. Landis、Shannon S. Stahl

  DOI：10.1021/acs.orglett.6b01598

  日期：2016.8.5

  aerobic oxidation of aldehydes to carboxylic acids has been developed using organic nitroxyl and NOx cocatalysts. KetoABNO (9-azabicyclo[3.3.1]nonan-3-one N-oxyl) and NaNO2 were identified as the optimal nitroxyl and NOx sources, respectively. The mildness of the reaction conditions enables sequential asymmetric hydroformylation of alkenes/aerobic aldehyde oxidation to access α-chiral carboxylic acids

  使用有机硝酰基和NO x助催化剂开发了一种将醛有氧氧化为羧酸的方法。KetoABNO（9-氮杂双环[3.3.1]壬南-3-酮N-氧基）和NaNO 2分别被确定为最佳硝酰基和NO x源。反应条件温和，能够连续进行烯烃不对称加氢甲酰化/需氧醛氧化，得到 α-手性羧酸，而无需外消旋化。使用一系列带有不同官能团的非手性醛进一步评估了氧化方法的范围、实用性和局限性。
• Microbial asymmetric decarboxylation of fluorine-containing arylmalonic acid derivatives
  作者：Kenji Miyamoto、Shigeo Tsuchiya、Hiromichi Ohta

  DOI：10.1016/s0022-1139(00)82414-8

  日期：1992.11

  α-Methyl-α-(trifluoromethylphenyl)malonic acids have been incubated with Alcaligenesbronchisepticus to afford optically active α-arylpropionic acids. Generally, the chemical and optical yields of the reaction products were higher when the substituents on the aromatic ring were strongly electron-withdrawing. Decarboxylation of α-fluoro-α- phenylmalonic acid with the aid of the same bacterium afforded

  已经将α-甲基-α-（三氟甲基苯基）丙二酸与支气管曲霉（Alcaligenes bronchisepticus）一起温育，以提供旋光性α-芳基丙酸。通常，当芳环上的取代基强烈吸电子时，反应产物的化学和光学产率较高。在相同细菌的帮助下，α-氟代-α-苯基丙二酸的脱羧得到光学活性的α-氟代-α-苯基乙酸。