A Room-Temperature Rh-Catalyzed Kinetic Resolution Pathway for Expedient Access to P-Stereogenic Cyclic Phosphinates

P-Stereogenic center-embedded heterocycles are privileged scaffolds in pharmaceuticals and catalysis, yet their synthesis remains a formidable challenge, largely reliant on desymmetrization or asymmetric aromatic C–P cross-coupling. Herein, we report a room temperature Rh-catalyzed enantioselective ring-closing hydrofunctionalization of alkynylphosphinates that directly constructs kinetically favored, nonarene-fused P-stereogenic five-membered rings. DFT calculations revealed that the proximal ligation of the phenolic additive plays a critical role in accelerating P–H bond activation, thereby enabling efficient hydrofunctionalization across the alkynyl segment. This method accommodates diverse substituents located at the phosphorus atom and the alkynyl moiety, providing a versatile platform for accessing valuable building blocks for pharmaceutical and chiral ligand design.