This review classifies and summarizes the past 10-15 years of advancements in the field of metal-involving (i.e., metal-mediated and metal-catalyzed) reactions of oximes. These reactions are diverse in nature and have been employed for syntheses of oxime-based metal complexes and cage-compounds, oxime functionalizations, and the preparation of new classes of organic species, in particular, a wide variety of heterocyclic systems spanning small 3-membered ring systems to macroheterocycles. This consideration gives a general outlook of reaction routes, mechanisms, and driving forces and underlines the potential of metal-involving conversions of oxime species for application in various fields of chemistry and draws attention to the emerging putative targets.

The dibenziodolium cation displays high catalytic activity for the Knorr-type reactions via binding with the carbonyl O atom.

Dibenziodolium and diphenyliodonium triflates display high catalytic activity for the multicomponent reaction that leads to a series of imidazopyridines. Density functional theory (DFT) calculations indicate that both the salts can play the role of hybrid hydrogen- and halogen-bond-donating organocatalysts, which electrophilically activate the carbonyl and imine groups during the reaction process. The ortho-H atoms in the vicinal position to the I atom play a dual role: forming additional noncovalent bonds with the ligated substrate and increasing the maximum electrostatic potential on the σ-hole at the iodine atom owing to the effects of polarization. Dibenziodolium triflate exhibits higher catalytic activity, and the results obtained from 1H nuclear magnetic resonance (NMR) titrations, in conjunction with those from DFT calculations, indicate that this could be explained in terms of the additional energy required for the rotation of the phenyl ring in the diphenyliodonium cation during ligation of the substrate.

Coordination Chemistry Reviews xxx (2016) pp. xxx-xxx Coordination chemistry and metal-involving reactions of amidoximes: Relevance to the chemistry of oximes and oxime ligands Dmitrii S. Bolotin, Nadezhda A. Bokach, Vadim Yu. Kukushkin * • Synthesis, properties, and identification of metal-free amidoximes. • Synthesis and structural features of amidoxime complexes. • Comparison of chemistry of amidoximes with that of conventional oximes. • Metal-mediated and metal-catalyzed reactions involving uncomplexed amidoximes. • Reactions of amidoxime ligands.

The most promising types of iodoazolium compounds exhibiting high catalytic activity toward halogen abstraction and carbonyl activation are highlighted.