Fatty Acid Derived Renewable Platform Chemicals via Selective Oxidation Processes

Abstract

Highly efficient synthesis processes for the selective catalytic oxidation of unsaturated fatty acid methyl esters (FAMEs) are described, leading to valuable renewable platform chemicals. Here keto-FAMEs derived from methyl oleate and methyl erucate were synthesized via a cocatalyst-free Wacker oxidation process using a high pressure reactor system. The catalytic system of palladium­(II) chloride in dimethylacetamide/water enabled the oxidation of monounsaturated FAMEs in the presence of molecular oxygen as sole reoxidant with reduced amounts of solvent in shorter reaction time compared to previous reports. The high product selectivity is confirmed by two different synthesis approaches and the characterization of thereof derived products using mass spectrometry measurements (GC-MS, ESI-MS-MS). The obtained keto-FAMEs are used in a subsequent Baeyer–Villiger oxidations with m-CPBA, enabling the synthesis of diesters, thus allowing access to various platform chemicals (e.g., hydroxy-esters, fatty alcohols). Moreover, an enone derivative, which can be obtained through selective photo peroxidation of methyl oleate, is studied in the cocatalyst-free Wacker oxidation process leading to a 1,3-diketone. Additionally, the same enone is used in the Baeyer–Villiger oxidation with Oxone and m-CPBA as oxidant, allowing the highly selective synthesis of a vinyl acetate and an epoxy diester derivative, respectively.

Recent progress in the catalytic transformation of carbon dioxide into biosourced organic carbonates

“…5) that find wide application as commodity chemicals, 171 biodiesel fuel, 172 and as intermediates for further chemical diversification. [173][174][175][176][177] In particular, epoxidized fatty acid esters (EFAs, Fig. 5) can be easily obtained and display potential for applications such as lubricants, additives and plasticizers.…”

Selective Wacker type oxidation of a macrocyclic diene to the corresponding monounsaturated ketone used as fragrance

“…12 When using N,N-dimethylacetamide (DMA) as solvent, which is supposed to stabilise the reduced palladium species, the oxidation with oxygen as green and sole oxidant proceeds without isomerisation of the double bond. 17 Further investigations showed broad substrate scope, functional group tolerance and high regioselectivity for this oxidation reaction, opening new strategies for the synthesis of biomolecules and other ne chemicals. 18 More recently, Sigman and co-workers developed a special designed Pd-catalyst for the Wacker type oxidation of internal olens.…”

CaO Catalyzed Transesterification of Ethyl 10-Undecenoate as a Model Reaction for Efficient Conversion of Plant Oils and Their Application to Depolymerization of Aliphatic Polyesters

“…Utilization of naturally abundant nonedible plant oils as attractive renewable feedstock has been considered as an important subject for a circular economy with decreasing concerns of global warming. − The efficient chemical modification of plant oils, fatty acids (FAs), and esters (FAEs) to biofuels − and aliphatic polyesters ,− ,− as well as fine chemicals ,,,,, has been recognized as the key subject. Many reports have thus been known concerning the catalytic transesterification of FAs and FAEs for the synthesis of biofuels ,− and fine chemicals. ,− ,− There are also reports concerning the catalysis for organic synthesis. − …”