Single-atom Rh catalysts present superior activity relative to homogeneous catalyst in olefins hydroformylation, yet with limited success in regioselectivity control. In the present work, we develop a phosphorus coordinated Rh1 single-atom catalyst with nanodiamond as support. Benefiting from this unique structure, the catalyst exhibits excellent activity and regioselectivity in hydroformylation of arylethylenes with wide substrate generality, i.e., with high conversion (>99%) and high regioselectivity (>90%), which is comparable with the homogeneous counterparts. The coordination interaction between Rh1 and surface phosphorus species is clarified by 31P solid-state NMR and X-ray absorption spectroscopy (XAS). Rh single atoms are firmly anchored over nanodiamond through Rh-P bonds, guaranteeing good stability in the hydroformation of styrene even after six runs. Finally, by using this catalyst, two kinds of pharmaceutical molecules, Ibuprofen and Fendiline, are synthesized efficiently with high yields, demonstrating a new prospect of single-atom catalyst in pharmaceutical synthesis.

Rhodium-catalyzed hydroaminomethylation of various vinyl arenes with anilines has been accomplished using water as an environmentally benign reaction media.

Straightforward access to 3‐aryl‐butyraldehydes was developed through the aqueous biphasic Rh‐catalyzed hydroformylation of 2‐arylpropenes using a water‐soluble PNP ligand. This protocol accommodates broad substrate scope with high yields (up to 95 %) and excellent linear selectivity (>99 : 1 b/l ratio). The synthesis of rac‐ar‐turmerone and the gram‐scale hydroformylation further demonstrated the practical nature of this method.