Cerium (IV) triflate-catalyzed selective oxidation of sulfides to sulfoxides with aqueous hydrogen peroxide

Scaled‐up, selective and green synthesis of sulfoxides under mild conditions using (CeIII‐MoVI)Ox/aniline hybrid rods as an efficient catalyst

“…[18][19][20][21][22][23][24][25] Moreover, overoxidation of the sulfoxides to sulfones is a common problem during the oxidation of sulfides [26,27] that has garnered attention from the synthetic community. [12,14,[46][47][48][49] In recent years, owing to the redox properties of ceria, various types of ceria-based catalysts including cerium (IV) triflate, [50] ammonium cerium (IV) nitrate, [51] immobilized cerium alkyl phosphonate [52] and heterobimetallic cerium (IV) oxo clusters [53] are also widely used in selective oxidation of sulfides. From an economical and environmental viewpoint, an acceptable process involving hydrogen peroxide (H 2 O 2 ) as a terminal oxidant in the presence of a catalyst would be at particular interest, [28,29] since hydrogen peroxide produces water as by-product and it is worth mentioning that a controlled partial oxidation is also dramatically easier than the most of other oxidants.…”

“…[30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] Despite the fact that amines such as aniline, pyridine and … are not an appropriate catalyst for the oxidation reactions, they can effectively modify the catalytic activity of the molybdates and molybdenum oxides due to the electronic interactions between these amines and the active sites in the hybrid structures. [12,14,[46][47][48][49] In recent years, owing to the redox properties of ceria, various types of ceria-based catalysts including cerium (IV) triflate, [50] ammonium cerium (IV) nitrate, [51] immobilized cerium alkyl phosphonate [52] and heterobimetallic cerium (IV) oxo clusters [53] are also widely used in selective oxidation of sulfides.…”

Recent Progress in the Selective Oxidation of Sulfides withHydrogen Peroxide

“…和取代苯甲酸盐相比 [49] , 体系中加入取代苯甲酸添 加剂 [50] , 亚砜的产率和 ee 值提高的幅度比较大, 分别可 以达到 36%～78%和 66%～95%. 以四氢呋喃作溶剂, 三氟甲磺酸铈可以催化 50%的 过氧化氢选择性地氧化硫醚为亚砜 [56] . 含有醇、醛、烯 烃、卤素、腈和酯等官能团的底物, 在反应过程中均不 受影响, 而且亚砜产率为 73%～96%.…”

Trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane as a novel and efficient reagent for selective sulfoxidation of sulfides under catalyst-free condition

“…Among these, aqueous H2O2 is a high atom-efficiency (47%) and most attractive oxidant in the green context as it is environmentally benign (only generates water as the by-product) and safe in operation [20]. However, H2O2 oxidizes sulfides rather slowly and therefore various kinds of acids such as AcOH [21], TBHP/p-TSA [22], and transition metal (Fe [23,24], Ti [25], Mo [26], V [27,28], W [29], Pt [30], Mn [31], Cu [32], Ru [33], Ta [34], Ce [35], Sc [36], Zr [37], and Cr [38]) based systems have been used to activate hydrogen peroxide. Many of these reagents and catalysts suffer from drawbacks such as long reaction times, low selectivity, low yields of products, and toxicity due to the formation of environmentally harmful waste by-products.…”