Pyridinylidenaminophosphines as Versatile Organocatalysts for CO2 Transformations into Value‐Added Chemicals

The carboxylative cyclization of propargylic alcohols with CO2 was developed employing pyridinylidenaminophosphines (PYA‐Ps) as organocatalyts for the first time. Moderate to good yields of α‐methylene cyclic carbonates were obtained with excellent chemo‐ and stereo‐selectivity. Density functional theory (DFT) calculations reveal that the catalytic reaction tends to proceed via the PYA‐Ps‐mediated basic ionic pair mechanism, and the intramolecular cyclization should be the rate determining step. Furthermore, the catalytic diversity of PYA‐Ps was investigated for the chemical transformations of CO2 to functionalized cyclic carbonates and N‐formylated amines. For the first time, pyridinylidenaminophosphines as organocatalysts were developed for diverse CO2 transformations to selectively synthesize value‐added cyclic carbonates and N‐formylated amines.