電子移動過程を基礎概念とする新しい有機合成

抄録

The following new synthetic methodologies involving electron transfer process have been developed. (1) Cleavage of the carbon-silicon bond : The carbon-silicon bonds in organopentafluorosilicates are cleaved by various oxidizing agents via initial electron transfer. The carbon-silicon bonds in allylsilanes and α-heteroatom substituted organosilicon compounds are also cleaved by electrochemical oxidation. (2) Indirect electrochemical oxidation using polymeric electron carrier such as poly (vinylpyridinium) bromide. (3) Cycloaddition of 1, 3-dicarbonyl compounds : The radical species generated by electrochemical oxidation of 1, 3-diketones adds to the olefin to give the formal [3 + 2] cycloadducts, dihydrofurans or tetrahydrofurans. In the presence of molecular oxygen the formal [2 + 2 + 2] cycloaddition of 1, 3-diketone, olefin and molecular oxygen takes place. The electroinitiated radical chain mechanism is proposed.