New Developments of the Principle of Vinylogy as Applied to π-Extended Enolate-Type Donor Systems

The principle of vinylogy states that the electronic effects of a functional group in a molecule are possibly transmitted to a distal position through interposed conjugated multiple bonds. As an emblematic case, the nucleophilic character of a pi- extended enolate-type chain system may be relayed from the legitimate alpha-site to the vinylogous gamma, epsilon, ..., omega remote carbon sites along the chain, provided that suitable HOMO-raising strategies are adopted to transform the unsaturated pronucleophilic precursors into the reactive polyenolate species. On the other hand, when "unnatural" carbonyl ipso-sites are activated as nucleophiles (umpolung), vinylogation extends the nucleophilic character to "unnatural" beta, delta, ... remote sites. Merging the principle of vinylogy with activation modalities and concepts such as iminium ion/enamine organocatalysis, NHC-organocatalysis, cooperative organo/metal catalysis, bifunctional organocatalysis, dicyanoalkylidene activation, and organocascade reactions represents an impressive step forward for all vinylogous transformations. This review article celebrates this evolutionary progress, by collecting, comparing, and critically describing the achievements made over the nine year period 2010-2018, in the generation of vinylogous enolate-type donor substrates and their use in chemical synthesis.