Metal-Involving Synthesis and Reactions of Oximes

Abstract

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.

tert‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis

“…Oximes are widely found in drugs such as pralidoxime, obidoxime and also widely used in dehydration reactions and 1,3 dipolar additions reactions. In organic and organometallic syntheses, oxime acts as a useful synthon for the preparations of many biologically active compounds …”

A Dimetallic Aminonitrone Nickel(II) Complex: Further Insights into Metal‐Mediated Nucleophilic Activation of Amidoximes

“…Amidoximes are an important class of organic compounds due to their wide utilization in organic synthesis and coordination and organometallic chemistry . Moreover, amidoximes exhibit versatile pharmacological activities, and can be applied in amidoxime‐based adsorption of heavy metal cationic species .…”

“…Moreover, amidoximes exhibit versatile pharmacological activities, and can be applied in amidoxime‐based adsorption of heavy metal cationic species . Previous reviews devoted to the metal‐free or metal‐mediated transformations of amidoximes indicates that a large number of such reactions proceed via O ‐functionalization of amidoxime species. Indeed, the generation of five‐, six‐, and seven‐membered heterocycles, reduction, or Tiemann rearrangement of amidoximes proceeds via alkylation or acylation of the HO moiety on the amidoxime species …”

Rhodium‐Catalysed [4+2] Annulation of Aromatic Oximes with Terminal Alkenes by C−H/N−O Functionalization towards 3,4‐Dihydroisoquinolines

“…[2,3] Despite substantial progress in the field, the development of highly atom-economic, sustainable routes that can achieve CÀ H functionalization under external-oxidizing-reagent-free conditions that release nontoxic waste products (e. g., H 2 O) remains a challenging area. [3][4][5][6] While the annulation of aromatic oximes with internal alkynes has been thoroughly investigated for the preparation of 3,4-disubstituted isoquinolines (Scheme 1a-i), [3,5] similar versions with alkenes are rare. [3][4][5][6] While the annulation of aromatic oximes with internal alkynes has been thoroughly investigated for the preparation of 3,4-disubstituted isoquinolines (Scheme 1a-i), [3,5] similar versions with alkenes are rare.…”