Regio- and stereo-selectivity of the first [3 + 2] cycloaddition of carbonyl oxide to electron-poor alkenes. Bidirectionality of the 1,3-dipole

Abstract

The carbonyl oxide (1), derived from the 2,3,7-trioxabicyclo[2.2.1]heptene (3) by thermal rearrangement, yields, as major products, methyl 1,2-dioxolane-4-carboxylate (8) and the novel tricyclic biperoxide (4)(whose structure was established by X-ray diffraction), by reaction with methyl acrylate and the acrylate (3) respectively, whereas it yields 5-ethoxy-1,2-dioxolane (9) with ethyl vinyl ether.