Tetramerization of 3-Methyl-cyclopropene-3-carbonitrile: A Novel CN-Alder-ene Reaction

At elevated temperatures 3-methyl-cyclopropene-3-carbonitrile <b>1</b> was found to tetramerize giving compound <b>2</b> (3-methyl-2,3-bis(2-t-methyl-2-c-cyanocyclopropyl)-1-(2-t-methyl-2-c,3-c-dicyanocyclopropyl)-cyclopropene) in good yields. This is the first example of Alder-ene type oligomerization of a 3,3-disubstituted cyclopropene. On the basis of the product geometry and stereoselective character of the reaction, a mechanism of formation of <b>2</b> involving CN-Alder-ene reaction was proposed. DFT modeling of the mechanism has shown that the CN-Alder-ene reaction is possible as a stepwise process involving a biradical intermediate.