Electro-Oxidative Coupling Reactions Leading to π-Conjugated Compounds

Electrochemical reactions are rapidly gaining attention today as a powerful and environmentally benign reaction processes for organic synthesis. We found that the electro-oxidation of palladium acetate afforded cationic palladium species and thus-generated cationic Pd species were efficient mediators for electro-oxidative coupling reactions. Homo-coupling of arylboronic acids and terminal alkynes proceeded efficiently to afford biaryls and butadiyne, respectively. Cross-coupling reactions between terminal alkynes and arylboronic acids were also achieved with the use of a Ag anode. As an advantage of electrochemical reactions, we developed a sequential reaction system switched between oxidative and neutral conditions by the on/off application of electricity, and several π-extended butadiynes were obtained in one-sequence by the system. Electrochemical intramolecular C−S coupling for the synthesis of thienoacene was also developed. The use of Bu₄NBr as a halogen mediator was essential for the reaction.