Since its discovery, the olefin metathesis (OM) reaction has found numerous applications in total synthesis, industrial processes, pharmaceutical, and material chemistry. Ruthenium (Ru), Molybdenum (Mo), and Tungsten (W)-based homogeneous catalysts are the most prominent due to their high activity and functional group stability. However, the transition to more abundant first-row metals, such as Vanadium (V), is desirable due to the low cost, decreased environmental footprint, and reduced toxicity. V alkylidenes are a promising class of compounds that have shown reactivity in OM, especially in ring-opening metathesis polymerization (ROMP) of cyclic olefins. However, those complexes found limited application in reactions with terminal olefins due to instability toward ethylene.FIU researchers have developed a method that enables the synthesis of a new class of V catalysts. This synthesis method produced the first catalytically active V oxo alkylidene, VO(CHSiMe3)(PEt3)2Cl, which exhibits high productivity with various terminal olefins in ring-closing metathesis (RCM) reactions. Additionally, the highly polarized V=C bond of this complex enables the regioselective formation of metallacyclobutane, resulting in reversible =CH2 transfer between terminal olefins without the formation of cross-products and ethylene, making this complex an ideal catalyst for carbon isotope exchange (CIE) performed directly on target molecules. Additional complexes are being synthesized and tested.
Olefin Metathesis:Cheaper: Vanadium is substantially less expensive than the rare metals that are currently used for OM.Decreased environmental footprint and reduced toxicity: purification, isolation, and recycling of currently used metals consume energy and generate a significant amount of waste.Superior performance compared to currently used catalysts.Carbon isotope exchange:Eliminates tedious, time-consuming, and costly practices where the development of new multi-step synthetic strategies for each specific target molecule is required.
Olefin Metathesis:Propylene production from ethylene and 2-butenes (Olefins Conversion Technology).Production of plasticizers and detergents precursors (Shell Higher Olefin Process).Synthesis of polymers, petrochemicals, agrochemicals, and conversion of low-molecular-weight alkanes to diesel fuel via “alkane metathesis”.Eco-friendly conversion of renewable seed oil feedstock into biofuel and linear alpha-olefins, that are utilized to produce cosmetics, soaps, detergents, polymer additives and coatings. Carbon isotope exchange: Incorporation of carbon isotopes directly into target compounds for metabolic and pharmacokinetic studies.Integration of carbon-11 into pharmaceuticals for positron emission tomography.
Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions. Dmitry S. Belov, Didac A. Fenoll, Indranil Chakraborty, Xavier Solans-Monfort, and Konstantin V. Bukhryakov. Organometallics 2021 40 (17), 2939-2944.Synthesis and Activity of Vanadium Oxo NHC Alkylidenes. Remarkable Preference for Degenerate Metathesis and Application for Carbon Isotope Exchange. Dmitry S. Belov, Carlos M. Acosta, Miquel Garcia-Molina, Kelly L. Rue, Xavier Solans-Monfort, and Konstantin V. Bukhryakov. Organometallics 2022 41 (21), 2897-2902.
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