Radical clocks as probes of 1,4-biradical intermediates in the photochemical cycloaddition reactions of 2-cyclopentenone with alkenes

Abstract

The products of the photochemical reaction of 2-cyclopentenone with 1,6-heptadiene and with vinylcyclopropane have been examined. With 1,6-heptadiene the products were cyclobutanes, which arise from 2 + 2 photocycloaddition between the cyclopentenone carbon–carbon double bond and one of the two terminal double bonds of the heptadiene. The 1,4-biradical that is an intermediate in this reaction contains a derivative of a 1-hexenyl radical; no products derived from cyclization of this intermediate to a cyclopentylmethyl radical were observed. With vinylcyclopropane some of the products isolated also arose from 2 + 2 photocycloaddition; in addition, comparable quantities of products resulting from rearrangement of the intermediate 1,4-biradical were obtained. In this case the initially produced intermediate 1,4-biradical contains a cyclopropylmethyl radical that can rearrange to a homoallylic radical; the products isolated were derived from intramolecular disproportionation in the new 1,7-biradical containing the homoallylic radical. The rate constant for the rearrangement of the cyclopropylmethyl radical to the homoallylic radical is known and was used as a clock to estimate the lifetime of the initially produced 1,4-biradical. The value estimated is of the order of 50 ns. The structures of the products indicate that the initial bonding between the excited cyclopentenone and vinylcyclopropane takes place at both the α-position and the β-position of the enone and not exclusively at the α-position as a recent report claims. Keywords: enone photocycloaddition, 1,4-biradicals, radical clocks.