Noble metal-free upgrading of multi-unsaturated biomass derivatives at room temperature: Silyl species enable reactivity

Biomass derivatives are a class of oxygen-rich organic compounds, which can be selectively upgraded to various value-added molecules by partial or complete hydrogenation over metal catalysts. Here, we show that Cs₂CO₃, a low-cost commercial chemical, enables the selective reduction of dicarbonyl compounds including bio-derived carboxides to monohydric esters/amides, hydroxylamines or diols with high yields (82-99%) at room temperature using eco-friendly and equivalent hydrosilane as a hydride donor. The in situ formation of silyl ether enables the developed catalytic system to tolerate other unsaturated groups and permits a wide substrate scope with high selectivities. Spectroscopic and computational studies elucidate reaction pathways with an emphasis on the role of endogenous siloxane.