Selective aerobic oxidation of hydrocarbons by molecular oxygen to afford valuable oxygen-containing functional compounds is a key challenge in modern chemical industry. Herein, an efficient catalytic system including metalloporphyrins as ideal catalysts and cumene as a co-substrate was developed for the aerobic oxidation of hydrocarbons to afford products with high yields and excellent chemoselectivities. Notably, this biomimetic process was found to be similar to cytochrome P450 monooxygenase-catalyzed reactions according to Michaelis–Menten kinetics. Experimental results and in situ monitoring techniques including the kinetic study, in situ ultraviolet–visible spectroscopy, and in situ electron spin resonance spectroscopy indicated that in situ generated cumyl hydroperoxide acted as an actual oxidant. Its formation was possibly mediated by metalloporphyrins to generate numerous free-radical species, and the high-valent Mn^IV–oxo π-cation radicals were regarded as active species in the aerobic oxidation. Consequently, both the co-substrate specificity and the possible reaction mechanism were systematically investigated based on the control experiments and results obtained from our previous studies.

通过分子氧对碳氢化合物进行选择性好氧氧化以提供有价值的含氧功能化合物是现代化学工业中的关键挑战。在此，开发了一种有效的催化体系，包括金属卟啉作为理想的催化剂和异丙基苯作为共底物，用于烃的需氧氧化，以提供具有高收率和优异的化学选择性的产物。值得注意的是，根据Michaelis-Menten动力学，这种仿生过程类似于细胞色素P450单加氧酶催化的反应。实验结果和原位监测技术（包括动力学研究，原位紫外-可见光谱和原位电子自旋共振光谱）表明：原位生成的氢过氧化枯基可作为一种实际的氧化剂。它的形成可能是由金属卟啉介导的，以产生许多自由基，高价的Mn ^IV-氧代π-阳离子自由基被认为是好氧氧化中的活性物种。因此，基于对照实验和我们先前研究获得的结果，系统地研究了共底物特异性和可能的​​反应机理。