Reaction Integration Using Electrochemically Generated Cationic Reactive Intermediates

Tuesday, May 13, 2014: 10:40
Floridian Ballroom D, Lobby Level (Hilton Orlando Bonnet Creek)
R. Hayashi, Y. Ashikari, A. Shimizu, T. Nokami, and J. I. Yoshida (Kyoto University)
From functional materials to biologically active compounds, the role of organic synthesis has been expanding continuously. Accordingly, the power and speed of organic synthesis should be enhanced to meet future demands for synthesis of various organic molecules. In this context, conventional step-by-step synthesis is being supplemented with integrated synthesis that combines multiple reactions in a single operation in one pot or in a flow system without isolating the intermediates.

In this presentation we report on time integration of electrochemical oxidation and chemical oxidation based on the “cation pool” method. For example, electrochemically generated carbocations are reacted with dimethylsulfoxide to give the corresponding alkoxysulfonium ions, which are well-known as key intermediates of Swern—Moffatt oxidation. The subsequent treatment with triethylamine gives the corresponding carbonyl compounds. Moreover, the reactions of halogenuim and arylchalcogenium cation pools stabilized by dimethoxysulfoxide with alkenes followed by treatment with triethylamine give a-halo and arylchalcogen-substituted carbonyl compounds, respectively.