The present review reports the current literature of the last 10 years on selective oxidation reactions of fatty acid derivatives and vegetable oils. The work is structured in divisions including epoxidation, radical oxidations, Wacker-type oxidation, dihydroxylation and C=C double bond cleavage.

Oxidation of unsaturated fatty acid derivatives and vegetable oils

Biomass is renewable and the most abundant carbon resource, and it shows great potential for sustainable production of chemicals in the future With respect to limited fossil reserves, biomass conv

Sustainable Productions of Organic Acids and Their Derivatives from Biomass via Selective Oxidative Cleavage of C-C bond

Recent advances in the field of selective epoxidation of vegetable oils and their derivatives: a review and perspective

During the last years, the industrial significance of renewable resources has highly increased. The ever-growing use of fossil resources for energy consumption, polymers, fine chemicals and pharmaceuticals and the therefore steadily increasing price favour the substitution of oil and gas by renewable resources. Here, especially products of catalytic functionalisations of vegetable fats and oils such as rapeseed oil, sunflower oil, palm oil or coconut oil play a decisive role. The present article gives a survey of several important catalytic functionalisations of fatty compounds and glycerol resulting in new attractive products. With their emerging properties, they could find a rapid introduction into the chemical market. Particularly the functionalisations via heterogeneous and homogeneous catalysis, like additions, reductions, oxidations and metathesis reactions, will be presented.

The refinement of renewable resources: new important derivatives of fatty acids and glycerol.

A multitude of synthesis methods for azelaic acid is evaluated in terms of feasibility and sustainability. Up to now, no alternative to industrially employed ozonolysis of oleic acid was developed.

Synthesis of azelaic acid from vegetable oil-based feedstocks

The present study considered the influence of various factors on the catalytic activity of systems based on a combination of tetrakis(oxodiperoxotungsto)phosphate(3−) with quaternary ammonium cations, for example, with methyltri-n-octylammonium [Me(n-C8H17)3N]+. The catalysts were tested in oxidation of cycloolefins (cyclohexene and cyclooctene), alcohols (octan-1-ol and phenylmethanol), and unsaturated fatty acids (cis-9-octadecenoic and 12-hydroxy-9Z-octadecenoic acids) with a 30% hydrogen peroxide solution. These reactions proceed under mild conditions (atmospheric pressure, 80–90 °C) to give carboxylic acids. The catalytic systems were characterized by vibrational (IR and Raman) spectroscopy. The state of the systems formed from various precursors, viz., polyoxometallates and phase-transfer catalysts, was studied. It was demonstrated for the first time that the structure formation of peroxo complexes depends on the nature of the halide anion of the quaternary ammonium salt used. The melting points of individual catalytic complexes were determined. The optimal conditions for oxidation were found.

Catalytic oxidation of olefins and alcohols with hydrogen peroxide in a two-phase system giving mono- and dicarboxylic acids

Methods for the synthesis of chiral organophosphorus compounds based on natural optically active compounds (hydroxy acids, amino acids and their derivatives, mono- and disaccharides, mono- and diterpenoids, steroids) are discussed. Particular attention is given to the synthesis of bisphosphines and bisphosphinites. These compounds serve as ligands for transition metal complexes, which catalyse asymmetric hydrogenation. Data on the enantioselectivity of hydrogenation of unsaturated precursors of amino acids and unsaturated prochiral acids as well as on information on the enantioselectivity of hydrosilylation of ketones are surveyed. The bibliography includes 77 references.

https://iopscience.iop.org/article/10.1070/RC2003v072n09ABEH000822/pdf

Natural compounds in the synthesis of chiral organophosphorous ligands

Selective oxidation of organic substrates by environment-friendly oxidizing agents is an important ingredient of the sustainable chemical industry. Here we report a comprehensive study in the field of metal peoroxocomplex catalysis for the selective liquid phase oxidation of various organic substrates. A number of well-defined bi-functional tungsten complex catalysts with tetra nuclear structure {PO4[WO(O2)2]4}3- in combination with a phase-transfer agents were synthesized. The structural properties were thoroughly studied using of IR, Raman and EXAFS spectroscopy. By combining different spectroscopy techniques were able to elucidate the effect of quaternary ammonium cations on the structural properties of the resulting peroxo complexes. The catalytic properties of these well-defined material were then evaluated in bi-phasic selective oxidation of cyclooctene, methyl oleate and N-phosphonomethyliminodiacetic acid with hydrogen peroxide under mild conditions. For every substrate we were able to achieve high conversion at the selectivity towards a target product close to 100%.

Tungsten Peroxopolyoxo Complexes as Advanced Catalysts for the Oxidation of Organic Compounds with Hydrogen Peroxide

Synthesis of new chiral phosphorous‐ and nitrogen‐containing ligands from resin acids

Catalysis via metal complexes has been studied using EXAFS and Raman spectroscopy. EXAFS studies have shown that in tungsten peroxocomplexes containing quaternary ammonium organic cation substitution affects the structure of anion {PO 4 [WO(O 2 ) 2 ] 4 } 3− . The last complex in series [Bu n 4 N] 3 {PO 4 [WO(O 2 ) 2 ] 4 }, [C 5 H 5 NCet] 3 {PO 4 [WO(O 2 ) 2 ] 4 } and [Et 2 Bn 2 N] 3 {PO 4 [WO(O 2 ) 2 ] 4 } demonstrates the most evident structure alteration. Vibration spectroscopy proves that structure conversion is related to the strength reduction of end double bond W O. As a result, antibate W O bond strength increases. That effect also changes the strength of tungsten bonding to cations. Synthesized catalytic complexes [Bu n 4 N] 3 {PO 4 [WO(O 2 ) 2 ] 4 } and [C 5 H 5 NCet] 3 {PO 4 [WO(O 2 ) 2 ] 4 } were tested in peucedanin oxidation by hydrogen peroxide. Oxidative catalytic transformation of above mentioned coumarin was shown to yield 2-hydorxyoreozelon, which is a bioactive compound used in medicine. Complex with cetylpyridinium cation appears to be the most active in this reaction.

Structure and properties of tungsten peroxopolyoxo complexes - promising catalysts for organics oxidation. II: Cation type influence on the tungsten peroxocomplex structure

T. B. Khlebnikova

Papers

Catalytic oxidation of olefins and alcohols with hydrogen peroxide in a two-phase system giving mono- and dicarboxylic acids

Natural compounds in the synthesis of chiral organophosphorous ligands

Tungsten Peroxopolyoxo Complexes as Advanced Catalysts for the Oxidation of Organic Compounds with Hydrogen Peroxide

Synthesis of new chiral phosphorous‐ and nitrogen‐containing ligands from resin acids

Structure and properties of tungsten peroxopolyoxo complexes - promising catalysts for organics oxidation. II: Cation type influence on the tungsten peroxocomplex structure