Tetramerization of 3-methyl-cyclopropene-3-carbonitrile: a novel CN-alder-ene reaction.
At elevated temperatures 3-methyl-cyclopropene-3-carbonitrile 1 was found to tetramerize giving compound 2 (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 2 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.
Ashirov
Roman V
RV
Department of Chemistry, RSU Immanuil Kant, Universitetskaya ul., 2, Kaliningrad 236040, Russia.
Shamov
Grigory A
GA
Lodochnikova
Olga A
OA
Litvynov
I A
IA
Appolonova
Svetlana A
SA
Plemenkov
Vitaly V
VV