INTRAMOLECULAR ANODIC OLEFIN COUPLING REACTIONS - THE USE OF BIS ENOL ETHER SUBSTRATES

In an effort to develop electrochemical methods for directly initiating oxidative cyclization reactions, the anodic oxidation of bis enol ether substrates has been examined. The reactions were found to lead to the formation of five-, six-, and seven-membered-ring 1,4-dicarbonyl equivalents. The reactions were not found to be useful for generating larger ring sizes. Both alkyl and silyl enol ether substrates were found to be compatible with the conditions required for carbon-carbon bond formation. Cyclic voltammetry studies indicated that the cyclizations were fast and that the reactions happened at or near the electrode surface. Finally, the cyclization reactions were shown to be compatible with the formation of quaternary carbons, even when carbon-carbon bond formation involved the generation of two vicinal quaternary carbons.