The cation pool method serves as a nice tool in electroorganic synthesis. Organic cations are electrochemically generated and accumulated in solution at low temperatures. Reactions with subsequently added nucleophiles give the desired products. However, the cation pool method cannot be applied to highly unstable cations that decompose during the course of the electrolysis. To expand the scope of the cation pool method, we have developed the stabilized cation pool method, in which organic cations stabilized by suitable stabilizing agents are electrochemically generated and accumulated in solution. The reactions of the stabilized organic cations with subsequently added nucleophiles give the desired products.

In this paper we show that C−H/aromatic C−H cross-coupling can be achieved by the electrochemical generation and accumulation of stabilized benzyl cations followed by their reactions with subsequently added aromatic nucleophiles. Beznylaminosulfonium ions as stabilized benzyl cations are generated and accumulated in the electrochemical oxidation of toluene derivatives. In the next step, the reactions with subsequently added electron-rich aromatic compounds as nucleophiles give the corresponding cross-coupled product. The method has been successfully applied to the synthesis of TP27, an inhibitor of PTPase. The reactions of benzylaminosulfonium ions with other carbon nucleophiles such as acetylacetone, ketene silyl acetals, allyltrimethylsilane, and trimethylsilylacetylene will also be discussed in the presentation.