INTRAMOLECULAR HOMOLYTIC DISPLACEMENTS .24. SIMPLE ACCESS TO GLYCIDICESTERS VIA INDUCED DECOMPOSITION OF PEROXYKETALS DERIVED FROM ETHYL 2-(1-HYDROPEROXYETHYL)PROPENOATE

The synthetic potential of the homolytic-induced decomposition of pero xyketals peroxyketals derived from ethyl 2-(1-hydroperoxyethyl)propeno ate to access glycidic esters was demonstrated. The propagation step o f this free radical chain reaction proceeds via the addition of an alk yl radical to the double bond followed by S(H)i on the peroxidic bond with the production of an oxy radical, regenerating rapidly by beta-el imination the alkyl radical responsible for the induced reaction, Thes e reactions of elimination produce two fragments, an alkyl radical and an ester molecule, from linear ''acetalic'' radical, or they could be isomerizations in the case of cyclanyloxy radicals. In these last cas es, the isomerization creates an ester function corresponding to a new protected functionality as aldehyde, acid, or alcohol.