Silver(I) as a widely applicable, homogeneous catalyst for aerobic oxidation of aldehydes toward carboxylic acids in water—“silver mirror”: From stoichiometric to catalytic

Abstract

A universal method for oxidation of aldehyde conducted by using atmospheric oxygen in water.

Silver‐Catalyzed Cross‐Coupling of Isocyanides and Active Methylene Compounds by a Radical Process

“…(2)].R egarding the C sp3 ÀHc arbamoylation of 1a with 4a,o xygenation of B leads to the hydroperoxide compound F.A fterwards,s ilver-promoted decomposition of F generates the oxyanion intermediate G and ah ydroxyl radical. [29] Thes of ormed hydroxyl radical could abstract ah ydrogen atom from 1a to generate A and H 2 Of or protonation of the intermediate G to produce the target product 5a.All the reactions belonging to any of these two categories proceed through silver(I)-initiated autocatalysis,and finally termination of the radical species A to 1a by oxidation of Ag(s) and subsequent proton abstraction from AgHCO 3 ,t hereby leading to the regeneration of Ag 2 CO 3 catalyst and completing the catalytic cycle.…”

A Supramolecular Catalyst Self-Assembled From Polyoxometalates and Cationic Pillar[5]arenes for the Room Temperature Oxidation of Aldehydes

“…The majority of these oxidation reactions in modern industry require stoichiometric amounts of hazardous oxidants such as KMnO 4 (Kleiderer, 1930 ; Ruhoff, 1936 ), CrO 3 (Sandborn, 1929 ), KHSO 5 (Mo, 2006 ), KIO 4 (Travis et al, 2003 ), etc., and often take place in organic solvents. Since Li et al sequentially reported first homogeneous silver- and copper- catalysis of aerobic aldehyde oxidation in water (Liu et al, 2015 ; Liu and Li, 2016 ), Wei et al reported a single-sided triol-functionalized iron centered Anderson POM catalysis (Yu et al, 2017 ). POMs combine high reactivity and stability in oxidation catalysis (Lechner et al, 2016 ).…”

Silver‐Catalyzed Cross‐Coupling of Isocyanides and Active Methylene Compounds by a Radical Process

“…[15e,26] In this process,A g 2 CO 3 plays the dual role as base and one-electron oxidant. [29] Thes of ormed hydroxyl radical could abstract ah ydrogen atom from 1a to generate A and H 2 Of or protonation of the intermediate G to produce the target product 5a.All the reactions belonging to any of these two categories proceed through silver(I)-initiated autocatalysis,and finally termination of the radical species A to 1a by oxidation of Ag(s) and subsequent proton abstraction from AgHCO 3 ,t hereby leading to the regeneration of Ag 2 CO 3 catalyst and completing the catalytic cycle. [6] Thefate of B,toafford either the enamine 3a or the tricarbonylmethane 5a,i sd irectly linked to the type of isocyanide.W hent he isonitrile is aromatic,f or example 1a, there are two possible paths for B to 3a conversion.…”