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

Biomass deriatives are a class of oxygen-rich organic compounds, which can be selectively upgraded to various value-added molecules by partial or complete hydrogeneration over metal catalysts. Here, we show that Cs2CO2, a low-cost commercial chemical, enables the selective reduction of dicarbonyl compounds including bio-derived carboxides to monohydric esteres/amides, hydroxylamines or diols with high yields (82-99%) at room temperature using eco-friendly and equivalent hydrosilane as 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 selectives. Spectroscopic and computational studies eludicate reaction pathways with an emphasis on the role of endogenous siloxane.