Hydrogen Cyanide Chemistry. 9. Cycloaddition Reactions and Nitrenium Ion Type Reactivity of Diiminosuccinonitrile

Article abstract of DOI:10.1021/jo00179a013

Cycloaddition reactions of diiminosuccinonitrile (DISN) with nucleophilic olefins yield a variety of products including <4+2> cycloadducts and aziridines.All of the products derived from 1,3-dienes, styrene, para-substituted styrenes, cycloheptatriene, norbornene, and norbornadiene can be accounted for by rearrangements of a common intermediate, zwitterionic aziridinium ion.We introduce the concept of reverse polarization and propose that DISN is a latent nitrenium ion source (isoelectronic with carbenes) and that reverse polarization of one of the >C=N bonds of DISNis responsible for the observed reactions.Comments are made on reverse polarization of other >C=X bonds, and facile 1,1-cycloreversion of aziridines is also reported.