Metal-organic frameworks enable regio- and stereo-selective functionalization of aldehydes and ketones

Selective C–C bond establishment from plentiful carbonyl compounds, which represents a crucial route to get the value-added products, is still far from satisfying both academic and industrial needs. Here, confirmed by both experiment and theoretical calculation, we report versatile and efficient asymmetric cross-coupling between carbonyl radicals (from aldehydes) and aryl radicals (from aryl halides) by adopting porous chiral metal-organic frameworks (MOFs) as catalysts under light illumination. In addition, these MOFs work well in catalyzing secondary amine-mediated asymmetric β- and α-carbonyl arylation of saturated aldehydes and ketones, thanks to the switchable features of both photoabsorbing metal-nitrogen clusters and chiral organic ligands inside MOFs. This work opens the avenue toward the rational design of heterogeneous catalysts for precise regio- and stereo-selective syntheses.