Recyclable Au0, Ag0 and Au0–Ag0 nanocolloids for the chemoselective hydrogenation of α,β-unsaturated aldehydes and ketones to allylic alcohols

A high-throughput evaluation of polymer-stabilized metal clusters, with varying composition and size, as unpromoted quasihomogeneous catalysts for the amide-phase hydrogenation of α,β-unsaturated aldehydes and ketones, allowed to identify the most appropriate metal clusters to achieve a high selectivity to allylic alcohols. Au0 and Ag0 based nanocolloids proved superior owing to their pronounced preference for CO reduction over CC saturation. Optimization of the metal nanoclusters in terms of size and composition led to exceptionally high allylic alcohol selectivities. These robust metal nanocolloids could be recycled efficiently from the amidic reaction media by solvent-resistant nanofiltration over cross-linked polyimide membranes. The catalytic activity of the optimized bimetallic nanocolloids consisting of alloyed Au and Ag was well preserved in successive hydrogenation runs while the chemoselectivity was unaffected. The wide substrate scope enabled to study the effect of the CCCO substitution pattern on the substrate reactivity and the allylic alcohol selectivity.

Au0 and Ag0 based nanocolloids emerge as superior quasihomogeneous metal catalysts for the amide-phase hydrogenation of α,β-unsaturated carbonyl compounds, owing to their pronounced preference for CO reduction. Colloidal Au0–Ag0 alloy clusters with optimized composition and size lead to the highest allylic alcohol yields and can be recycled efficiently by solvent-resistant nanofiltration over custom-made polyimide membranes with unaffected hydrogenation chemoselectivity. Figure optionsDownload as PowerPoint slide