Abstract
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.
Benefit
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.
Market Application
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 metathesisâ€쳌.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.
Publications
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.
Brochure
