Alkylated Sesamol Derivatives as Potent Antioxidants

Sesamol is a phenolic derivative. Its antioxidant activity is low than that of Trolox and depends on benzodioxole moiety. Thus, a molecular modification strategy through alkylation, inspired by natural and synthetic antioxidants, was studied by molecular modeling at the DFT/B3LYP level of theory by comparing the 6-31+G(d,p) and 6-311++G(2d,2p) basis sets. All proposed derivatives were compared to classical related antioxidants such as Trolox, t-butylated hydroxytoluene (BHT) and t-butylated hydroxyanisole (BHA). According to our results, molecular orbitals, single electron or hydrogen-atom transfers, spin density distributions, and alkyl substitutions at the ortho positions related to phenol moiety were found to be more effective than any other positions. The trimethylated derivative was more potent than Trolox. t-Butylated derivatives were stronger than all other alkylated derivatives and may be new alternative forms of modified antioxidants from natural products with applications in the chemical, pharmaceutical, and food industries.

Site-selective remote C(sp3)–H heteroarylation of amides via organic photoredox catalysis

Radical translocation processes triggered by nitrogen-centered radicals (NCRs), such as 1,5-hydrogen atom transfers (1,5-HAT), demonstrated by the well-established Hofmann-Löffler-Freytag (HLF) reaction, provide an attractive approach for the controllable and selective functionalization of remote inert C(sp3)–H bonds. Here we report an amidyl radical-triggered site-selective remote C(sp3)–H heteroarylation of amides under organic photoredox conditions. This approach provides a mild and highly regioselective reaction affording remote C(sp3)–H heteroarylated amides at room temperature under transition-metal free, weakly basic, and redox-neutral conditions. Non-prefunctionalized heteroarenes, such as purines, thiazolopyridines, benzoxazole, benzothiazoles, benzothiophene, benzofuran, thiazoles and quinoxalines, can be alkylated directly. Sequential and orthogonal C–H functionalization of different heteroarenes by taking advantage pH value or polarity of radicals has also been achieved. DFT calculations explain and can predict the site-selectivity and reactivity of this reaction. This strategy expands the scope of the Minisci reaction and serves as its alternative and potential complement.

Atmospheric reactions of glyoxal with NO2 and NH2 radicals: Hydrogen abstraction mechanism and natural bond orbital analysis

Glyoxal can be important in atmospheric chemistry in terms of its ability to convert to secondary organic aerosols. In this study, the glyoxal-breaking reaction by two atmospheric active radicals, NO2 and NH2, has been investigated at the B3LYP and M06-2X levels in connection with 6-311++G(d,p) basis set. The formation of the most stable adducts from glyoxal with NO2/NH2 radical requires two hydrogen atom transfers. The accuracy of the predicted mechanisms in describing the hydrogen transfers was confirmed by atoms-in-molecules calculations and natural bond orbital analysis. The calculated results predict that hydrogen transfer process in both reactions at the M06-2X level is favourable from the kinetic and thermodynamic points of view. In the natural bond orbital analysis, the stabilization energy, E(2), delocalization corrections, at the B3LYP level is much higher than the same results at the M06-2X level (nearly twice). The activation thermodynamic parameters show that the first steps of the two reactions have lower barrier energy than the second steps. The Gibbs free energy values estimate that adducts of both the reactions at the mentioned method are spontaneous. The whole reaction of glyoxal + NH2 is more favourable than the whole reaction of glyoxal + NO2. The rate constants were calculated for the mentioned pathways using transition state theory for bimolecular steps and the fitted equations are reported.