Aziridination via Nitrogen-Atom Transfer to Olefins from Photoexcited Azoxy-Triazenes.

Herein, we report that readily accessible azoxy-triazenes can serve as nitrogen atom sources under visible light excitation for the phthalimido-protected aziridination of alkenes. This approach eliminates the need for external oxidants, precious transition metals, and photocatalysts, marking a departure from conventional methods. The versatility of this transformation extends to the selective aziridination of both activated and unactivated multisubstituted alkenes of varying electronic profiles. Notably, this process avoids the formation of competing C-H insertion products. The described protocol is operationally simple, scalable, and adaptable to photoflow conditions. Mechanistic studies support the idea that the photofragmentation of azoxy-triazenes results in the generation of a free singlet nitrene. Furthermore, a mild photoredox-catalyzed N-N cleavage of the protecting group to furnish the free aziridines is reported. Our findings contribute to the advancement of sustainable and practical methodologies for the synthesis of nitrogen-containing compounds, showcasing the potential for broader applications in synthetic chemistry.

Photoinduced Nitroarenes as Versatile Anaerobic Oxidants for Accessing Carbonyl and Imine Derivatives.

Herein, we report a protocol for the anaerobic oxidation of alcohols, amines, aldehydes, and imines promoted by photoexcited nitroarenes. Mechanistic studies support the idea that photoexcited nitroarenes undergo double hydrogen atom transfer (HAT) steps with alcohols and amines to provide the respective ketone and imine products. In the presence of aldehydes and imines, successive HAT and oxygen atom transfer (OAT) events occur to yield carboxylic acids and amides, respectively. This transformation is amenable to a continuous-photoflow setup, which led to reduced reaction times.

Cascade Synthesis of Phenanthrenes under Photoirradiation.

We report a photoinduced phenanthrene synthesis from aryl iodides and styrenes through an arylation/cyclization cascade. Compared to prior methods, this approach obviates the need for hazardous reagents and provides access to unsymmetrical phenanthrenes with good functional group tolerance. Mechanistic studies revealed that photoexcitation of aryl iodides leads to homolytic C-I bond cleavage. Arylation of styrenes with the formed aryl radical species furnishes stilbene derivatives, which undergo photoinduced cyclization promoted by iodine generated in situ to yield phenanthrene products.

Role of surface chemistry and morphology in the reactive adsorption of H2S on iron (hydr)oxide/graphite oxide composites.

Composites of magnetite and two-line ferrihydrite with graphite oxide (GO) were synthesized and tested as hydrogen sulfide adsorbents. Exhausted and initial composites were characterized by the adsorption of nitrogen, X-ray diffraction, potentiometric titration, thermal analysis, and FTIR. The addition of GO increased the surface area of the composites due to the formation of new micropores. The extent of the increase depended on the nature of the iron (hydr)oxide and the content of GO. The addition of GO did not considerably change the crystal structure but increased the number of acidic functional groups. While for the magnetite composites an increase in the H2S adsorption capacity after GO addition was found, the opposite effect was recorded for the ferrihydrite composites. That increase in the adsorption capacity was linked to the affinity of the composites to adsorb water in mesopores of specific sizes in which the reaction with basic surface groups takes place. Elemental sulfur and ferric and ferrous sulfates were detected on the surface of the exhausted samples. A redox reactive adsorption mechanism is proposed to govern the retention of hydrogen sulfide on the surface of the composites. The incorporation of GO enhances the chemical retention of H2S due to the incorporation of OH reactive groups and an increase in surface heterogeneity.