24/01/2024

Apeiron Synthesis in Journal of the American Chemical Society

 

The significance of ethenolysis resides in its remarkable potential: it presents a viable route to generate valuable chemicals while simultaneously tackling the urgent imperative of sustainability.

For instance, the reaction yields linear α-olefins (LAO) and 9-decenoic acid methyl ester (9-DAME). This way, vegetable oil - with global production amounting to around 208.8 million metric tons in 2021/22 - and animal oils can be turned into polymers, specialty chemicals, and new compounds.

While the theoretical underpinnings of ethenolysis are now well understood, its industrial applications lag. Ethylene, central to the reaction, tends to destabilize ruthenium complexes, which are crucial for catalysis. This instability posed significant challenges, making large-scale, cost-effective applications elusive.

In our laboratory, we have worked on optimizing the catalysts used in ethenolysis. The goal has always been clear: achieve higher efficiency, broader substrate compatibility, and enhanced stability. Our research focused on ruthenium metathesis catalysts, especially those integrated with Cyclic(Alkyl)(Amino)Carbene (CAAC) ligands. By introducing a spirocyclic motif to the CAAC ligand backbone, we've not only enhanced the catalyst's stability but also significantly bolstered its efficiency.

  • To quantify, our catalysts have achieved a staggering Turn-Over Number (TON) exceeding 900,000 and 700,000 with 0.5 ppm catalyst loading in reactions with fatty acid methyl esters from high oleic sunflower oil (comprising 93.0% methyl oleate) and rapeseed oil (with 68.6% methyl oleate) respectively.
  • For pure methyl oleate, TON exceeds 2,600,000 with a mere 0.1 ppm catalyst loading.

These catalysts have showcased exceptional efficiency, opening pathways for large-scale industrial applications. Ethenolysis has enormous potential for sustainable use cases, offering a path to reducing fossil fuel dependency. Moreover, from an economic standpoint, the optimized efficiency and stability of the reaction can lead to significant cost savings in industrial applications, making it a win-win for both the environment and industry.

Apeiron Synthesis team of researchers led by Rafał Gawin, have achieved a significant breakthrough in chemical engineering by developing new ruthenium olefin metathesis catalysts that effectively inhibit decomposition pathways, a discovery that is set to revolutionize the ethenolysis process. Detailed in their study "Inhibition of the Decomposition Pathways of Ruthenium Olefin Metathesis Catalysts: Development of Highly Efficient Catalysts for Ethenolysis," these catalysts address the long-standing challenge of rapid decomposition, thereby greatly enhancing efficiency and durability.

 

R. Gawin, A. Tracz, P. Krajczy, A. Kozakiewicz-Piekarz, J. P. Martínez, B. Trzaskowski "Inhibition of the Decomposition Pathways of Ruthenium Olefin Metathesis Catalysts: Development of Highly Efficient Catalysts for Ethenolysis" J. Am. Chem. Soc., 145, 45, 25010–25021 (2023).