Organic Synthesis Using Electroauxiliaries

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We propose a new concept of electroauxiliary as a useful tool in electron transfer-driven reactions. Electroauxiliaries activate reactant molecules to facilitate the electron transfer process and also control the chemical process of thus generated reactive species to give desired products selectively.We have found that silicon, tin, and sulfur serve as excellent electroauxiliaries for the oxidation of heteroatom compounds. The concept of electroauxiliary was found to be useful for oxidative carbon-carbon bond formation of heteroatom compounds. Several electrooxidative carbon-carbon bond formation reactions using tin and sulfur as electroauxiliaries have been developed.This concept was also found to be site-selective transformation of organic compounds because we can easily distinguish between electroauxiliaries at different sites of molecule using the difference of their redox potential.We also investigated the mechanism of the action of electroauxiliaries. In the case of silicon and tin, the electron transfer is accelerated by the interaction of the carbon-metal sigma orbital with the nonbonding porbital of the heteroatom which raises the HOMO level. In the case of sulfur, however, such interaction was not observed and the electron transfer was found to take place mainly from the sulfur atom.