Aerobic Copper-Catalyzed Oxysulfonylation of Vinylarenes with Sodium Sulfinates under Mild Conditions: A Modular Synthesis of ß-Ketosulfones.

An aerobic copper-catalyzed oxysulfonylation of vinylarenes with sodium sulfinates is described. This protocol features mild reaction conditions, convenient operation, and broad substrate scope with respect to vinylarenes and sodium sulfinates. Notably, the protocol demonstrates excellent tolerance of functional groups such as chloro, bromo, ester, cyano, and nitro groups. Mechanistic investigations indicated that the reaction should undergo radical cascades involving a sulfonyl radical generated from sodium sulfinate with air as the terminal oxidant, addition across alkene to deliver a benzylic radical, and subsequent cross-coupling with air.

Nickel-Catalyzed Direct Sulfonylation of Styrenes and Unactivated Aliphatic Alkenes with Sulfonyl Chlorides.

A nickel-catalyzed direct sulfonylation of alkenes with sulfonyl chlorides has been developed using 1,10-phenanthroline-5,6-dione as the ligand. Unactivated alkenes and styrenes including 1,1-, 1,2-disubstituted alkenes can be subjected to the protocol, and a wide range of vinyl sulfones was obtained in high to excellent yields with good functional group compatibility. Notably, the process did not allow the desulfonylation of sulfonyl chloride or chlorosulfonylation of alkenes. Radical-trapping experiment supported that a sulfonyl free-radical was likely produced and triggered subsequent transformation in the process.

Salen-Based Conjugated Microporous Polymers for Efficient Oxygen Evolution Reaction.

Exploring high-performance electrocatalysts, especially non-noble metal electrocatalysts, for the oxygen evolution reaction (OER) is critical to energy storage and conversion. Herein, we report for the first time that conjugated microporous polymers (CMPs) incorporating salen can be used as OER electrocatalysts with outstanding performances. The best OER electrocatalyst (salen-CMP-Fe-3) exhibits a low Tafel slope of 63 mV dec-1 and an overpotential of 238 mV at 10 mA cm-2 . DFT and Grand Canonical Monte Carlo calculations confirmed that the significantly improved electrocatalytic properties can be attributed to the intrinsic catalytic activity of the salen moiety and the enrichment effect of the pore structures. This work demonstrates that salen-based conjugated polymers are a type of metal-coordinated porous polymer that show excellent catalyst performance.