Electrochemical Nickel Catalysis for Sp-Sp Cross-Electrophile Coupling Reactions of Unactivated Alkyl Halides.

A constant-current electrochemical method for reducing catalytic nickel complexes in sp-sp cross-electrophile coupling reactions has been developed. The electrochemical reduction provides reliable nickel catalyst activation and turnover and offers a tunable parameter for reaction optimization, in contrast to more standard activated metal powder reductants. The electrochemical reactions give yields (i.

Solvolysis, Electrochemistry, and Development of Synthetic Building Blocks from Sawdust.

Either aldehyde or cinnamyl ether products can be selectively extracted from raw sawdust by controlling the temperature and pressure of a solvolysis reaction. These materials have been used as platform chemicals for the synthesis of 15 different synthetic substrates. The conversion of the initial sawdust-derived materials into electron-rich aryl substrates often requires the use of oxidation and reduction chemistry, and the role electrochemistry can play as a sustainable method for these transformations has been defined.

Photovoltaic-driven organic electrosynthesis and efforts toward more sustainable oxidation reactions.

The combination of visible light, photovoltaics, and electrochemistry provides a convenient, inexpensive platform for conducting a wide variety of sustainable oxidation reactions. The approach presented in this article is compatible with both direct and indirect oxidation reactions, avoids the need for a stoichiometric oxidant, and leads to hydrogen gas as the only byproduct from the corresponding reduction reaction.

Oxidative cyclization reactions: controlling the course of a radical cation-derived reaction with the use of a second nucleophile.

Construction of new ring systems: Oxidative cyclizations (see picture; RVC=reticulated vitreous carbon) have been conducted that use two separate intramolecular nucleophiles to trap an enol ether-derived radical cation intermediate. The reactions provide a means for rapidly trapping the radical cation intermediate in a manner that avoids competitive decomposition reactions.

Anodic coupling of carboxylic acids to electron-rich double bonds: A surprising non-Kolbe pathway to lactones.

Carboxylic acids have been electro-oxidatively coupled to electron-rich olefins to form lactones. Kolbe decarboxylation does not appear to be a significant competing pathway. Experimental results indicate that oxidation occurs at the olefin and that the reaction proceeds through a radical cation intermediate.