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Catalytic oxidation of α-substituted cyclohexanone with steric hindrance to 6-oxohexanoic acid involved during the total synthesis of (+)-biotin
Applied Catalysis A: General ( IF 4.7 ) Pub Date : 2021-08-05 , DOI: 10.1016/j.apcata.2021.118304
Qiyi Ma 1, 2 , Haoran Yuan 1, 2 , Jianyong Mao 3 , Jia Yao 1 , Haoran Li 1, 2, 4
Affiliation  

A homogeneous catalyst system FeCl3/DMSO was developed to catalyze α-substituted cyclohexanone to corresponding 6-oxohexanoic acid, an important intermediate involved during the synthesis of (+)-biotin. A highly efficient oxidation with 95.3 % of conversion and 88.0 % of selectivity was achieved using oxygen as the oxidant, which shows great advantage over the traditional peroxide method from industrial aspects. The detailed reaction process was evaluated to determine the parallel reactions scheme consisted by two oxidative reactions and one chlorination reaction. The [Fe(DMSO)4Cl2]Cl complex detected by UV–vis and FT-IR spectrometer was proposed as the active component during the catalytic process. The control experiments, capture of important intermediates, and kinetic study were performed, which showed the oxidation proceeded via the combination of ionic and radical pathway. The FeCl3/DMSO can be recycled with minor yield loss.



中文翻译:

(+)-生物素全合成过程中α-取代环己酮对6-氧代己酸的空间位阻催化氧化

开发了均相催化剂体系 FeCl 3 /DMSO 以将 α-取代的环己酮催化为相应的 6-氧代己酸,6-氧代己酸是 (+)-生物素合成过程中涉及的重要中间体。使用氧气作为氧化剂实现了转化率为95.3%和选择性为88.0%的高效氧化,这在工业方面显示出优于传统过氧化物方法的巨大优势。对详细的反应过程进行了评估,以确定由两个氧化反应和一个氯化反应组成的平行反应方案。[Fe(DMSO) 4 Cl 2由紫外-可见光和红外光谱仪检测到的]Cl 络合物被提议作为催化过程中的活性成分。进行了对照实验、重要中间体的捕获和动力学研究,表明氧化是通过离子和自由基途径的结合进行的。FeCl 3 /DMSO 可以回收,收率损失很小。

更新日期:2021-08-10
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