Catalytic Decarbonylation of Biosourced Substrates

Abstract

Linear α-olefins (LAO) are one of the main targets in the field of surfactants, lubricants, and polymers. With the depletion of petroleum resources, the production of LAO from renewable feedstocks has gained increasing interest in recent years. In the present study, we demonstrated that Ir catalysts were suitable to decarbonylate a wide range of biosourced substrates under rather mild conditions (160 °C, 5 h reaction time) in the presence of potassium iodide and acetic anhydride. The resulting LAO were obtained with good conversion and selectivity provided that the purity of the substrate, the nature of the ligand, and the amounts of the additives were controlled accurately. The catalytic system could be recovered efficiently by using a Kugelrohr distillation apparatus and recycled.

Selective production of linear α-olefins via catalytic deoxygenation of fatty acids and derivatives

“…While there have been experimental studies of decarbonylation dehydration using a range of different metals, including Ir [69][70][71] and the more abundant Fe 72 and Ni [73][74][75] , the highest catalytic activity has been observed by using Pd and Rh. 49,60,[62][63] Pd has shown higher activity, but Rh on the other hand has not required a large excess of ligand to ensure activity and selectivity and is thus attractive from an atom-economic point of view.…”

“…Another additive used in different experiments is KI, which may play part in a ligand exchange with chloride for [M]Cl type catalysts. [70][71][72]…”

“…The progress has mainly been towards improving the palladium catalyzed reaction by varying the ligand and reducing the reaction temperature and the procedure has also shown promise for application in multistep synthesis. [61][62][63][64][65][66][67][68] Alternative metals like iridium [69][70][71] and the more earth-abundant options iron 72 and nickel [73][74][75] have also been investigated.…”

The Pivotal Role of Catalysis in France: Selected Examples of Recent Advances and Future Prospects.

“…Among the research axes, catalytic approaches, including new chemo‐ and biocatalytic systems are developed, including their one‐pot combination under the new concept of hybrid catalysis . Since the program launch year (2012), many results have been obtained, some of which have been now disclosed after a patenting process, with the resultant portfolio of efficiently developed reactions such as the conversion of glycerol to added value products such as glycolic or glyceric acid, including raw glycerol reactivity, as well as conversion to divinylglycol; direct conversion of alcohols to carboxylic acids, as well as to cerides/symmetrical esters; hydroformylation of triglycerides in a self‐emulsifying medium; synthesis of conjugated dienyl derivatives by green bisallylic substitution; decarbonylation of fatty acids; selective polyol dehydration. Another large project in the field of catalyst development for biosourced application is REALCAT, “Advanced high throughput technologies platform for biorefineries catalysts design”, which consists of a high‐throughput platform, unique in the world, devoted to innovation in heterogeneous, homogeneous, bio‐, and hybrid catalysis.…”

The Mechanism of Rh-Catalyzed Transformation of Fatty Acids to Linear Alpha olefins

“…With this promising outlook, transition-metal catalysts based on palladium [12][13][14][15]22,25,29,30,32], rhodium [14,23], iridium [27,33], nickel, [24,34], and iron [28] have been developed. Palladium-based catalysts have so far reached the highest activities [14].…”