Water-assisted electron capture exceeds photorecombination in biological conditions.

A decade ago, an electron-attachment process called interatomic Coulombic electron capture has been predicted to be possible through energy transfer to a nearby neighbor. It has been estimated to be competitive with environment-independent photorecombination, but its general relevance has yet to be established. Here, we evaluate the capability of alkali and alkaline earth metal cations to capture a free electron by assistance from a nearby water molecule.

Photocatalyzed Transition-Metal-Free Oxidative Cross-Coupling Reactions of Tetraorganoborates*.

Readily accessible tetraorganoborate salts undergo selective coupling reactions under blue light irradiation in the presence of catalytic amounts of transition-metal-free acridinium photocatalysts to furnish unsymmetrical biaryls, heterobiaryls and arylated olefins. This represents an interesting conceptual approach to forge C-C bonds between aryl, heteroaryl and alkenyl groups under smooth photochemical conditions. Computational studies were conducted to investigate the mechanism of the transformation.

Electro-Olefination-A Catalyst Free Stereoconvergent Strategy for the Functionalization of Alkenes.

Conventional methods carrying out C(sp )-C(sp ) bond formations are typically mediated by transition-metal-based catalysts. Herein, we conceptualize a complementary avenue to access such bonds by exploiting the potential of electrochemistry in combination with organoboron chemistry. We demonstrate a transition metal catalyst-free electrocoupling between (hetero)aryls and alkenes through readily available alkenyl-tri(hetero)aryl borate salts (ATBs) in a stereoconvergent fashion.

Electrochemical Synthesis of Biaryls via Oxidative Intramolecular Coupling of Tetra(hetero)arylborates.

We report herein versatile, transition metal-free and additive-free (hetero)aryl-aryl coupling reactions promoted by the oxidative electrocoupling of unsymmetrical tetra(hetero)arylborates (TABs) prepared from ligand-exchange reactions on potassium trifluoroarylborates. Exploiting the power of electrochemical oxidations, this method complements the existing organoboron toolbox. We demonstrate the broad scope, scalability, and robustness of this unconventional catalyst-free transformation, leading to functionalized biaryls and ultimately furnishing drug-like small molecules, as well as late stage derivatization of natural compounds.