Recent advances in electro-organic chemistry involving miniaturization, integration, and combinatorial chemistry were reviewed. Microelectrode array technology for site-selective electro-organic reactions and addressable libraries provides a direct and unlabeled method for measuring small-molecule-protein interactions. Electrochemical systems using solid-supported bases and acids ("site separation") can realize electrolysis without the addition of supporting electrolytes. Well-designed "bipolar electrodes" have enabled the production of patterned gradient polymer brushes and microfibers. For the display of combinatorial organic electrochemistry, batch and flow electrolysis systems for the optimization and screening of electro-organic reactions as well as the building of chemical libraries for organic compounds are described.

Electrochemical decarboxylation of aryloxyacetic acids followed by fluorination provides easy access to fluoromethyl aryl ethers.

The first Cu-catalyzed dehydrogenative C–O cyclization for the synthesis of furan-fused thienoacenes is described. A variety of heteroacenes including a thieno­[3,2-b]­furan or a thieno­[2,3-b]­furan skeleton were synthesized by intramolecular C–H/O–H coupling. The use of a mixed solvent of N-methyl-2-pyrrolidone, ethylene glycol monomethyl ether, and toluene was essential for suppressing side reactions and efficiently promoting the reaction. Double C–O cyclization was also conducted to afford highly π-expanded furan-fused thienoacenes.

The first electrochemical synthesis of diarylphosphole oxides (DPOs) was achieved under mild conditions. The practical protocol employs commercially available and inexpensive DABCO as a hydrogen atom transfer (HAT) mediator, leading to various DPOs in moderate to good yields. This procedure can also be applied to the synthesis of six-membered phosphacycles, such as phenophosphazine derivatives. Mechanistic studies suggested that the reaction proceeds via an electro-generated phosphinyl radical.

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