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Site‐selective C(sp3)−H functionalization of unreactive hydrocarbons is always challenging due to its inherited chemical inertness, slightly different reactivity of various C−H bonds, and intrinsically high bond dissociation energies. Here, a site‐selective C−H alkylation of naphthoquinone with unactivated hydrocarbons using Mn2(CO)10 as a catalyst under blue‐light (457 nm) irradiation without any external acid or base and pre‐functionalization is presented. The selective C−H functionalization of tertiary over secondary and secondary over primary C(sp3)−H bonds in abundant chemical feedstocks was achieved, and hydroxylation of quinones was realized in situ by employing the developed methodology. This protocol provides a new catalytic system for the direct construction of high‐value‐added compounds, namely, parvaquone (a commercially available drug used to treat theileriosis) and its derivatives under ambient reaction conditions. Moreover, this operationally simple protocol applies to various linear‐, branched‐, and cyclo‐alkanes with high degrees of site selectivity under blue‐light irradiated conditions and could provide rapid and straightforward access to versatile methodologies for upgrading feedstock chemicals. Mechanistic insight by radical trapping, radical scavenging, EPR, and other controlled experiments well corroborated with DFT studies suggest that the reaction proceeds by a radical pathway. [ABSTRACT FROM AUTHOR]

To date, organoseleniums are pre-eminent for peroxide decomposition and radical quenching antioxidant activities. On the contrary, here, a series of Janus-faced aminophenolic diselenides have been prepared from substituted 2-iodoaniline and selenium powder using copper-catalyzed methodology. Subsequently, condensation with substituted salicylaldehyde afforded the Schiff base, which on reduction, yielded the desired substituted aminophenolic diselenides in 72%–88% yields. The generation of reactive oxygen species (ROS) from oxygen gas by the synthesized aminophenolic diselenides was studied by analyzing the oxidation of dichlorofluorescein diacetate (DCFDA) dye and para-nitro-thiophenol by fluorescence and UV-Visible spectroscopic methods. Furthermore, density functional theory calculations and crystal structure analysis revealed the role of functional amine and hydroxyl sites present in the Janus-faced organoselenium catalyst for the activation of molecular oxygen, where NH and phenolic groups bring the oxygen molecule close to the catalyst by N–H⋯O and O–H⋯O intermolecular interactions. Additionally, these functionalities stabilize the selenium-centered radical in the formed transition states. Antioxidant activities of the synthesized diselenides have been explored as the catalyst for the decomposition of hydrogen peroxide using benzenethiol sacrificial co-reductant by a well-established thiol assay. Radical quenching antioxidant activity was studied by the quenching of DPPH radicals at 516 nm by UV-Visible spectroscopy. The structure activity correlation suggests that the electron-rich phenol and electron-rich and sterically hindered selenium center enhance the oxidizing property of the aminophenolic diselenides. Janus-faced diselenides were also evaluated for their cytotoxic effect on HeLa cancer cells via MTT assay, which suggests that the compounds are effective at 15–18 μM concentration against cancer cells. Moreover, the combination with therapeutic anticancer drugs Erlotinib and Doxorubicin showed promising cytotoxicity at the nanomolar concentration (8–28 nM), which is sufficient to suppress the growth of the cancer cells. [ABSTRACT FROM AUTHOR]