The catalytic oxidation of cycloalkanes using molecular oxygen employing porphyrin cobalt(II) as catalyst was enhanced through use of cycloalkyl hydroperoxides, which are the primary intermediates in oxidation of cycloalkanes, as additional oxidants to further oxidize cycloalkanes in the presence of porphyrin copper(II), especially for cyclohexane, for which the selectivity was enhanced from 88.6 to 97.2% to the KA oil; at the same time, the conversion of cyclohexane was enhanced from 3.88 to 4.41%. The enhanced efficiency and selectivity were mainly attributed to the avoided autoxidation of cycloalkanes and efficient utilization of oxidation intermediate cycloalkyl hydroperoxides as additional oxidants instead of conventional thermal decomposition. In addition to cyclohexane, the protocol presented in this research is also very applicable in the oxidation of other cycloalkanes such as cyclooctane, cycloheptane and cyclopentane, and can serve as a applicable and efficient strategy to boost the conversion and selectivity simultaneously in oxidation of alkanes. This work also is a very important reference for the extensive application of metalloporphyrins in catalysis chemistry.

中文翻译：

---

氧化中间体高效利用卟啉钴(II)催化氧化环烷烃

使用卟啉钴 (II) 作为催化剂的分子氧催化氧化环烷烃通过使用环烷基过氧化氢（环烷烃氧化的主要中间体）作为额外氧化剂在卟啉铜 (II) 存在下进一步氧化环烷烃得到增强，尤其是环己烷，对KA油的选择性从88.6%提高到97.2%；同时，环己烷的转化率从3.88%提高到4.41%。效率和选择性的提高主要归因于避免了环烷烃的自氧化和有效利用氧化中间体环烷基氢过氧化物作为额外的氧化剂，而不是传统的热分解。除了环己烷，本研究中提出的方案也非常适用于其他环烷烃的氧化，如环辛烷、环庚烷和环戊烷，可作为一种适用且有效的策略，同时提高烷烃氧化的转化率和选择性。该工作对于金属卟啉在催化化学中的广泛应用也是非常重要的参考。