Preserving precise choreography of bonds in Z-stereoretentive olefin metathesis by using quinoxaline-2,3-dithiolate ligand.

Abstract

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.