50390-51-7Relevant articles and documents
Synthesis of novel chiral heterometallic terpene oximates: Unusual generation of an aluminium enolate by a cooperative effect
Fernández-Millán, María,Temprado, Manuel,Cano, Jesús,Cuenca, Tomás,Mosquera, Marta E.G.
, p. 10514 - 10518 (2016)
Al-K heterometallic terpene oximate derivatives with uncommon structural features are reported. These species react with an aryl ketone leading to heterometallic enolates via an unusual route. Isolation of a remarkable heterometallic Al-K enolate confirms the cooperative mechanism proposed by DFT calculations, where the oximate ligand has a prominent role. From these enolates the formation of new C-C bonds is straightforward.
Competitive Desulfonylative Reduction and Oxidation of α-Sulfonylketones Promoted by Photoinduced Electron Transfer with 2-Hydroxyaryl-1,3-dimethylbenzimidazolines under Air
Hasegawa, Eietsu,Nakamura, Shyota,Oomori, Kazuki,Tanaka, Tsukasa,Iwamoto, Hajime,Wakamatsu, Kan
, p. 2556 - 2569 (2021/02/27)
Desulfonylation reactions of α-sulfonylketones promoted by photoinduced electron transfer with 2-hydroxyarylbenzimidazolines (BIH-ArOH) were investigated. Under aerobic conditions, photoexcited 2-hydroxynaphthylbenzimidazoline (BIH-NapOH) promotes competitive reduction (forming alkylketones) and oxidation (producing α-hydroxyketones) of sulfonylketones through pathways involving the intermediacy of α-ketoalkyl radicals. The results of an examination of the effects of solvents, radical trapping reagents, substituents of sulfonylketones, and a variety of hydroxyaryl- and aryl-benzimidazolines (BIH-ArOH and BIH-Ar) suggest that the oxidation products are produced by dissociation of α-ketoalkyl radicals from the initially formed solvent-caged radical ion pairs followed by reaction with molecular oxygen. In addition, the observations indicate that the reduction products are generated by proton or hydrogen atom transfer in solvent-caged radical ion pairs derived from benzimidazolines and sulfonylketones. The results also suggest that arylsulfinate anions arising by carbon-sulfur bond cleavage of sulfonylketone radical anions act as reductants in the oxidation pathway to convert initially formed α-hydroperoxyketones to α-hydroxyketones. Finally, density functional theory calculations were performed to explore the structures and properties of radical ions of sulfonylketones as well as BIH-NapOH.
External-oxidant-free amino-benzoyloxylation of unactivated alkenes of unsaturated ketoximes with: O -benzoylhydroxylamines
Chen, Jiangfei,Zhu, Yan-Ping,Li, Jin-Heng,Wang, Qiu-An
supporting information, p. 5215 - 5218 (2021/05/31)
A new copper-catalyzed two-component amino-benzoyloxylation of unactivated alkenes of unsaturated ketoximes with O-benzoylhydroxylamines as the benzoyloxy sources is developed. Chemoselectivity of this method toward amino-benzoyloxylation or oxy-benzoyloxylation of alkenyl ketoximes relies on the position of the tethered olefins, and provides an external-oxidant-free alkene difunctionalization route that directly utilizes O-benzoylhydroxylamines as the benzoyloxy radical precursors and internal oxidants for the divergent synthesis of cyclic nitrones and isoxazolines.