Intermediates Formed in the Reactions of Organocuprates with α,β‐Unsaturated Nitriles

Conjugate additions of organocuprates are of outstanding importance for organic synthesis. To improve our mechanistic understanding of these reactions, we have used electrospray ionization mass spectrometry for the identification of the ionic intermediates formed upon the treatment of LiCuR₂ ? LiCN (R=Me, Bu, Ph) with a series of α,β‐unsaturated nitriles. Acrylonitrile, the weakest Michael acceptor included, did not afford any detectable intermediates. Fumaronitrile (FN) yielded adducts of the type Li_n?1Cu_nR_2n(FN)_n^?, n=1–3. When subjected to fragmentation in the gas phase, these adducts were not converted into the conjugate addition products, but re‐dissociated into the reactants. In contrast, the reaction with 1,1‐dicyanoethylene furnished the products of the conjugate addition without any observable intermediates. Tri‐ and tetracyanoethylene proved to be quite reactive as well. The presence of several cyano groups in these substrates opened up reaction pathways different from simple conjugate additions, however, and led to dimerization and substitution reactions. Moreover, the gas‐phase fragmentation behavior of the species formed from these substrates indicated the occurrence of single‐electron transfer processes. Additional quantum‐chemical calculations provided insight into the structures and stabilities of the observed intermediates and their consecutive reactions.