Zwitterionic structure is necessary for Ni complexes to catalyze carbonylative polymerization (COP) of cyclic ethers. The cationic charge at the Ni center imparts sufficient electrophilicity to the Ni-acyl bond for it to react with cyclic ethers to give an acyl-cyclic ether oxonium intermediate, while the ligand-centered anionic charge ensures that the resultant oxonium cation is ion-paired with the Ni nucleophile. The current catalysts give non-alternating copolymers of carbon monoxide and cyclic ethers and are the most effective when both ethylene oxide and tetrahydrofuran are present as the cyclic ether monomers.

A rhodium-catalyzed transarylation of benzamides via selective C–C bond activation with arylboronic acids was described, which was distinct from the conventional metal-catalyzed C–N bond activation. This transformation exhibited good functional group compatibility with yields up to 88%, offering a practical approach for the construction and functionalization of benzamides. Preliminary experimental and computational studies revealed the selectivity of metal insertion into the C–C bond or the C–N bond was greatly affected by substituents on the amide’s N atom.

A rhodium-catalyzed Suzuki–Miyaura coupling reaction via C­(O)-C bond activation to form 2-benzoylpyridine N-oxide derivatives is reported. Both the C­(O)–C­(sp2) and C­(O)–C­(sp3) bond could be activated during the reaction with yields up to 92%. The N-oxide moiety could be employed as a traceless directing group, leading to free pyridine ketones.

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An efficient transformation of trifluoromethylated compounds to monofluoroalkenes was developed through Pd-catalyzed selective defluorinative sulfenylation. A variety of α-fluorovinylthioethers were prepared in good yields from α-trifluoromethylated benzyl bromides and odorless...