Selective iron-catalyzed aerobic oxidation of alcohols in water to carboxylic acids mediated by additives. Issue 17 (16th August 2022)

• Record Type: Journal Article
• Authors: Yu, Han; Ren, Jingjing; Xie, Ya; Su, Xiaofang; Wang, Aiping; Yan, Likai; Jiang, Feng; Wei, Yongge
• Is Part Of: Green chemistry. Volume 24:Issue 17(2022)
• Page Start: 6511
• Page End: 6516
• Publication Date: 2022-08-16
• Subjects: Environmental chemistry -- Industrial applications -- Periodicals; Environmental management -- Periodicals; 660
• DOI: 10.1039/d2gc01447e
• Languages: English
• ISSNs: 1463-9262

Abstract

Abstract : The iron catalyst (POM-Fe) could combine with chloride ions to form a supramolecular aggregate FeMo6 ·Cl, which was used in the oxidation of alcohols to carboxylic acids under mild conditions and can tolerate 40 substrates with moderate to high yield. Abstract : The direct catalytic oxidation of alcohols to carboxylic acids is very appealing, however, economic and environmentally friendly catalytic systems should be further explored from the aspect of less waste production and a convenient procedure. Herein, we display a structurally defined inorganic ligand-supported iron compound, (TBA)3 [FeMo6 O18 (OH)6 ] (simplified as FeMo6 ), which could be used as a heterogeneous molecular catalyst in water for this conversion, with oxygen as the terminal oxidant and KCl as an additive. The oxidation of various alcohols (aromatic and aliphatic) could be achieved in almost all cases under mild conditions and provided the corresponding carboxylic acids in high yields, including some active molecular entities and natural molecules with carboxyl structures. Detailed studies showed that chloride ions could combine with the molecular catalyst FeMo6 to form a supramolecular aggregate FeMo6 ·Cl, which could effectively catalyze the reaction, relying on the synergistic effect of chloride ions and FeMo6 . Control experiments, 1 H NMR studies and density functional theory (DFT) calculations showed that the oxidation reaction might involve a free radical pathway.