Synthesis of ω-functionalized ketones from strained cyclic alcohols by ring-opening and cross-recombination between alkyl and N-oxyl radicals.

Radical ring-opening oxyimidation of cyclobutanols and cyclopropanols with the formation of ω-functionalized ketones was discovered. The oxidative C-O coupling proceeds via the interception of a primary alkyl radical generated from a cyclic alcohol with a reactive radical generated in situ, which is an electron-deficient N-oxyl radical. The developed conditions allow for the balanced generation rates of carbon- and N-oxyl radicals, which are necessary for their selective cross-recombination. Thus, typical competitive dimerization processes of carbon-centered radicals, their intermolecular cyclization, and N-oxyl radical self-decay are suppressed. The method is applicable to a wide range of cyclobutanols and results in oxyimidated ketones in yields of up to 82%.

The diacetyliminoxyl radical in oxidative functionalization of alkenes.

The intermolecular oxime radical addition to CC bonds was observed and studied for the first time. The diacetyliminoxyl radical was proposed as a model radical reagent for the study of oxime radical reactivity towards unsaturated substrates, which is important in the light of the active development of synthetic applications of oxime radicals. In the present work it was found that the diacetyliminoxyl radical reacts with vinylarenes and conjugated dienes to give radical addition products, whereas unconjugated alkenes can undergo radical addition or allylic hydrogen substitution by diacetyliminoxyl depending on the substrate structure. Remarkably, substituted alkenes give high yields of C-O coupling products despite the significant steric hindrance, whereas unsubstituted alkenes give lower yields of the C-O coupling products. The observed atypical C-O coupling yield dependence on the alkene structure was explained by the discovered ability of the diacetyliminoxyl radical to attack alkenes with the formation of a C-N bond instead of a C-O bond giving side products. This side process is not expected for sterically hindered alkenes due to lower steric availability of the N-atom in diacetyliminoxyl than that of the O-atom.

C-O Coupling of Hydrazones with Diacetyliminoxyl Radical Leading to Azo Oxime Ethers-Novel Antifungal Agents.

Selective oxidative C-O coupling of hydrazones with diacetyliminoxyl is demonstrated, in which diacetyliminoxyl plays a dual role. It is an oxidant (hydrogen atom acceptor) and an O-partner for the oxidative coupling. The reaction is completed within 15-30 min at room temperature, is compatible with a broad scope of hydrazones, provides high yields in most cases, and requires no additives, which makes it robust and practical. The proposed reaction leads to the novel structural family of azo compounds, azo oxime ethers, which were discovered to be highly potent fungicides against a broad spectrum of phytopathogenic fungi (Venturia inaequalis, Rhizoctonia solani, Fusarium oxysporum, Fusarium moniliforme, Bipolaris sorokiniana, Sclerotinia sclerotiorum).