Novel Reactivities on tert-Butyldimethylsilyl and tert-Butyldiphenylsilyl Ethers : Application to the Synthesis of 11-epi-PGF_2a

Abstract

A facile 1, 5-migration of tert-butyldimethylsilyl and tert-butyldiphenylsilyl groups in the Witting reaction and under other basic conditions was observed during synthetic studies on prostaglandins. A new method for the cleavage of these two silyl protecting groups to the parent alcohol was developed by the combined use of potassium superoxide and crown ether in dimethyl sulfoxide. Utilizing these new reactivities, an efficient synthesis of 11-epi-PGF_2α from the well known Corey lactone was successfully achieved.