Grzesiński Łukasz, Nadirova Maryana, Guschlbauer Jannick, Brotons-Rufes Artur, Poater Albert, Kajetanowicz Anna, Grela Karol
Biological and Chemical Research Centre, Faculty of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02-089, Warsaw, Poland.
Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, c/ Mª Aurèlia Capmany 69, 17003, Girona, Catalonia, Spain.
Nat Commun. 2024 Oct 17;15(1):8981. doi: 10.1038/s41467-024-52876-4.
The Z-alkene geometry is prevalent in various chemical compounds, including numerous building blocks, fine chemicals, and natural products. Unfortunately, established Mo, W, and Ru Z-selective catalysts lose their selectivity at high temperatures required for industrial processes like reactive distillation, which limits their synthetic applications. To address this issue, we develop a catalyst capable of providing Z-alkenes with high selectivity under harsh conditions. Our research reveals a dithiolate ligand that, stabilised by resonance, delivers high selectivity at temperatures up to 150 °C in concentrated mixtures. This distinguishes the dithioquinoxaline complex from existing Z-selective catalysts. Notably, this trait does not compromise the new catalyst's usability under classical conditions, matching the activity of known stereoretentive catalysts. Density Functional Theory calculations were employed to understand the reaction mechanism and selectivity, and to investigate the poisoning that the catalyst may undergo and how it competes with catalytic activity. Furthermore, the quinoxaline-based catalyst enables the valorisation of bio-sourced alkene feedstocks and the production of agricultural sex pheromones for pest control.
Z-烯烃几何构型在各种化合物中普遍存在，包括众多的结构单元、精细化学品和天然产物。不幸的是，现有的钼、钨和钌Z-选择性催化剂在诸如反应精馏等工业过程所需的高温下会失去其选择性，这限制了它们的合成应用。为了解决这个问题，我们开发了一种能够在苛刻条件下以高选择性提供Z-烯烃的催化剂。我们的研究揭示了一种二硫醇盐配体，它通过共振稳定，在浓缩混合物中高达150°C的温度下具有高选择性。这使二硫代喹喔啉配合物与现有的Z-选择性催化剂有所不同。值得注意的是，这一特性并不影响新催化剂在经典条件下的可用性，其活性与已知的立体保持催化剂相当。采用密度泛函理论计算来理解反应机理和选择性，并研究催化剂可能遭受的中毒情况以及它如何与催化活性竞争。此外，基于喹喔啉的催化剂能够实现生物来源烯烃原料的增值利用，并生产用于害虫防治的农业性信息素。
