Azaphosphatrane/Ag2O catalyzed the carboxylative cyclization of propargylic alcohols and CO2

•The PMB-AZAP/Ag2O was first applied to the carboxylative cyclization of propargylic alcohols with CO2 and achieved high yield (>99 %) and selectivity (>99 %) of the α-alkylidene cyclic carbonates at room temperature and atmospheric pressure.•The reaction mechanism revealed that PMB-AZAP and Ag2O formed a silver complex PMB-AZAP-Ag during the reaction, which was a key active species for catalytic carboxylative cyclization.•The PMB-AZAP/Ag2O was also applied for the one-pot reaction of propargylic alcohol, CO2 and CH3OH, affording the β-carbonyl carbonate with high yield of 80 %.