Photoredox-Catalysis-Modulated, Nickel-Catalyzed Divergent Difunctionalization of Ethylene

Abstract

Functionalization of ethylene without polymerization is challenging under photoirradiation conditions. We have demonstrated that the photo-transformation of ethylene can be controllable by merging photoredox and transition-metal catalysis. In our study, the use of different photoredox catalysts was able to modulate the oxidation state of the nickel catalyst. Through different oxidation states, the nickel-catalyzed couplings proceeded via distinct pathways to generate divergent ethylene difunctionalization products selectively from the same feedstock.

Selective Late‐Stage Oxygenation of Sulfides with Ground‐State Oxygen by Uranyl Photocatalysis

“…Having established the powerful and selective synthetic method for the generation of sulfones and sulfoxides and the modification of pharmaceuticals, we explored the intrinsic mechanism. First, labeling experiments with H 2 18 O and 18 O 2 unambiguously confirmed that the oxygen atoms on the sulfoxides and sulfones originated from the oxygen atmosphere and not from water (Section SVI‐1).…”

Selective Late‐Stage Oxygenation of Sulfides with Ground‐State Oxygen by Uranyl Photocatalysis

“…Having established the powerful and selective synthetic method [29] for the generation of sulfones and sulfoxides and the modification of pharmaceuticals,weexplored the intrinsic mechanism. First, labeling experiments with H 2 18 Oa nd 18 O 2 unambiguously confirmed that the oxygen atoms on the sulfoxides and sulfones originated from the oxygen atmosphere and not from water (Section SVI-1).…”

Recent advances in photoredox and nickel dual-catalyzed cascade reactions: pushing the boundaries of complexity

“…Recently, Wu and coworkers reported a photoredox/nickel catalyzed difunctionalization of ethylene with aryl halides in the presence of a stoichiometric amount of organic reductants, affording 1,2-diarylethanes with good efficiency (Scheme 19). 29 In this process, the oxidative addition of an active catalyst Ni I with an aryl halide would give an aryl-Ni III species, which undergoes migratory insertion of ethylene to generate a cationic alkyl-Ni III species with the dissociation of a halide ligand. Mechanistic studies and DFT calculations provided support for this proposed pathway.…”