Electrochemical Synthesis of Sultone Derivatives via Dehydrogenative C-O Bond Formation.

Electrochemical dehydrogenative C-O bond formation for the synthesis of sultones was achieved. In the presence of KCO and HO, constant current electrolysis of [1,1'-biphenyl]-2-sulfonyl chloride afforded an aryl-fused sultone quantitatively. Under the optimized conditions, a variety of sultone derivatives were obtained.

Metal-free electrochemical fluorodecarboxylation of aryloxyacetic acids to fluoromethyl aryl ethers.

Electrochemical decarboxylation of aryloxyacetic acids followed by fluorination provides easy access to fluoromethyl aryl ethers. This electrochemical fluorodecarboxylation offers a sustainable approach with electric current as traceless oxidant. Using EtN·5HF as fluoride source and as supporting electrolyte, this simple electrosynthesis affords various fluoromethoxyarenes in yields up to 85%.

Cu-Catalyzed Dehydrogenative C-O Cyclization for the Synthesis of Furan-Fused Thienoacenes.

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-]furan or a thieno[2,3-]furan skeleton were synthesized by intramolecular C-H/O-H coupling. The use of a mixed solvent of -methyl-2-pyrrolidone, ethylene glycol monomethyl ether, and toluene was essential for suppressing side reactions and efficiently promoting the reaction.

Electrosynthesis of Phosphacycles via Dehydrogenative C-P Bond Formation Using DABCO as a Mediator.

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.

Miniaturization and Combinatorial Approach in Organic Electrochemistry.

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.

Synthesis of 3-Benzo[b]thienyl 3-Thienyl Ether via an Addition-Elimination Reaction and Its Transformation to an Oxygen-Fused Dithiophene Skeleton: Synthesis and Properties of Benzodithienofuran and Its π-Extended Derivatives.

The synthesis of 3-benzo[b]thienyl 3-thienyl ether and its dehydrogenative cyclization leading to benzodithienofuran (BDTF; [1]benzothieno[3,2-b]thieno[2,3-d]furan) are described for the first time. Further transformation of BDTF to more π-extended BDTF derivatives and their fundamental physical properties are also studied.