Alcoholysis of Epoxides Catalyzed by Tetracyanoethylene and Dicyanoketene Acetals

Abstract
A typical π-acid tetracyanoethylene and capto-dative olefin dicyanoketene acetals were found to catalyze stereospecific alcoholysis of epoxides at the ambient temperature to 50 °C in good yields. Mildness and significant chemoselectivity of the catalysts were demonstrated by intactness of tetrahydropyranyl ether and ethylene acetal groups. A novel regioselectivity associated with anchimeric assistance of the ethereal group on the side chain was observed in the ring opening reaction of the 1,2-disubstituted epoxides.

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