Oxidation of olefins with H2O2 catalyzed by gallium(III) nitrate and aluminum(III) nitrate in solution

Effect of aluminum vacancies on the H2O2 or H2O interaction with a gamma‐AlOOH surface. A solid‐state DFT study

“…Hydrogen peroxide oxygenation of saturated and unsaturated hydrocarbons in the presence of heterogeneous alumina catalysts have been reported . It was demonstrated that Al(III) salts can also act as homogeneous catalysts for olefin epoxidation and alkane hydroperoxydation . The covalent binding of H 2 O 2 to the catalytic center was studied only for homogeneous systems within cluster approaches .…”

Catalytic Oxidation Processes for the Upgrading of Terpenes: State-of-the-Art and Future Trends

“…Gallium and aluminum catalysts. Recently, Shul'pin and coworkers [24] used soluble gallium nitrate salts as catalysts in the epoxidation of carvone 27 and limonene 2 with hydrogen peroxide and compared the results to aluminum analogs. Both metals lead to a 60% conversion in 3 h at 80 °C, with In 2012, a practical method catalyzed by a a Mn(II) salt, combined with pyridine-2-carboxylic acid (PCA) and substoichiometric butanedione, was used in the oxidation of some terpenes with H 2 O 2 as oxidant [23] and proved to be particularly relevant for acid-or base-sensitive epoxide products.…”

“…Gallium and aluminum catalysts. Recently, Shul'pin and coworkers [24] used soluble gallium nitrate salts as catalysts in the epoxidation of carvone 27 and limonene 2 with hydrogen peroxide and compared the results to aluminum analogs. Both metals lead to a 60% conversion in 3 h at 80 • C, with a mass balance of 65%, which could be explained by the formation of other volatile products.…”

“…Gallium vs. Aluminum salts. Conditions: Carvone (1.0 M) with H2O2 (4.0 M) containing 3.2 M H2O, Catalyst (0.02 M), Ethylacetate, 80 °C (adapted from reference[24]).…”

Diastereoselective Synthesis of 7,8-Carvone Epoxides

“…For these reasons, the interest in the synthesis of the 7,8-epoxides of carvone using catalysis has increased. Many metals have been used in this catalysed oxidation reaction: gallium [12]; aluminium [12]; vanadium and tungsten [13]; and di-or tetracoordinated metals with diamines, mainly manganese [14][15][16] (Scheme 1) or iron [17][18][19][20], or chitosan based with manganese, copper, cobalt, or nickel [21]. In all cases, the diastereoselectivity was very small or even negligible.…”