An intermolecular 1,2-diacylation of alkenes is disclosed via cooperative N-heterocyclic carbene and photoredox catalysis under the mediation of PPh 3 and Cs 2 CO 3 . This protocol provides a practical approach for construction of 1,4-dicarbonyl compounds toward novel diketone and pharmaceutical derivatives. Furthermore, the regioselective dicarbonyl compounds can be synthesized by adding acyl azolium salt. Mechanistic investigations suggest that the process was a critical radical/radical cross coupling of ketyl radicals with benzylic C-radicals.

Porphyrin metal organic frameworks has been extensively studied in recent years due to its excellent photocatalytic property. In this work, we successfully prepared a novel bismuth-based porphyrin metal organic frameworks...

Selective reduction of nitroaromatics to the corresponding amines generally requires complex conditions, involving pressurized hydrogen, higher temperatures, or organic acids. In this work, we successfully prepared a series of porphyrin-based MOF photocatalysts (Pd-PMOFs, In-PMOFs, and In/Pd-PMOFs) via a facile solvothermal method for the efficient selective reduction of nitroaromatics to corresponding anilines with deionized water as the hydrogen donor. Being a new structured material (monoclinic, C52H40InN6O8Pd), on account of the abundant pore channels, strong light absorption capability, well-matched bandgap, as well as the coordination of indium ions and palladium ions, In/Pd-MOFs have excellent migration efficiency of photo-induced electrons and holes. Specifically, the In/Pd-PMOF photocatalyst manifested superior conversion (100%) and selectivity (≥80%) toward the screened nitro compounds under mild conditions. This work avoids the use of strong reductants, organic acids, and pressurized hydrogen gas as hydrogen sources, providing a promising concept for developing green catalytic systems.

Porphyrin‐based MOFs have great structural tunability and prominent catalyst activity. In this work, a series of antimony porphyrin MOFs (PCN‐224(Sb)‐L) were synthesized to efficiently selective oxidate benzyl alcohol under visible light. To investigate the effects of the Sb‐axial ligands on photocatalytic activity, the oxidation of benzyl alcohol to corresponding benzaldehyde was utilized as a model reaction. Within these three analogues of PCN‐224(Sb)‐L, PCN‐224(Sb)‐OH exhibit a remarkable 96 % conversation and 100 % selectivity of the benzaldehyde with an extremely high turnover number (TON) of 9300.

An intermolecular direct α-C–H acylation of alkenes was revealed by the visible-light-mediated N-heterocyclic carbene and quinuclidine catalysis. This convenient protocol provides a facile synthesis toward novel natural products and drug derivatives of α-substituted vinyl ketones. Mechanistic investigations indicated that the transformation proceeded via sequential radical addition, radical coupling, and an elimination process.