The catalytic synthesis of cyclic carbonates via the cycloaddition of CO2 to epoxides is a standard methodology for CO2 fixation.For this purpose,chiral basket-handle porphyrin-Co complexes were devised,prepared,and f...The catalytic synthesis of cyclic carbonates via the cycloaddition of CO2 to epoxides is a standard methodology for CO2 fixation.For this purpose,chiral basket-handle porphyrin-Co complexes were devised,prepared,and fully characterized by nuclear magnetic resonance,mass spectrometry,Fourier transform infrared spectroscopy,ultraviolet-visible spectroscopy,and specific rotation.The proposed metalloporphyrin catalysts were synthesized with either 1,1'-bi-2-naphthol or L-phenylalanine,which have different chirality,and then applied to the coupling of propylene oxide and CO2 for generating chiral cyclic carbonates with good enantioselectivity under extremely mild conditions in the presence of tetrabutyl ammonium chloride as a co-catalyst.The good enantioselectivity in the cycloaddition reaction is attributed to a synergistic interplay between the chiral porphyrin catalysts and the substrate.The mechanism and enantioselectivity of the asymmetric cycloaddition reaction is discussed.展开更多
A series of zwitterionic‐type quaternary ammoniums(ZTQAs)with varying lengths of alkyl chains combined with KI were synthesized and considered as catalysts for the coupling reaction of CO2 and various terminal epoxid...A series of zwitterionic‐type quaternary ammoniums(ZTQAs)with varying lengths of alkyl chains combined with KI were synthesized and considered as catalysts for the coupling reaction of CO2 and various terminal epoxides.The prolonged alkyl chain of ZTQAs exhibited temperature‐responsive self‐separation in propylene carbonate(PC).The interaction between ZTQAs and KI was confirmed by X‐ray photoelectron spectroscopy and quantum chemical calculations.This interaction strengthened the nucleophilicity of the I?ion,favoring the catalytic reaction.The 3‐(dimethyltetradecylammonium)propane sulfonate(DTPS)/KI showed an excellent yield of PC(95.1%)at 125°C,1.5 MPa,and 1 mol%loading of catalyst.The precipitate formed spontaneously from the catalytic system,providing high catalytic activity of the homogeneous catalyst,as well as easy recovery of the heterogeneous catalyst.展开更多
文摘The catalytic synthesis of cyclic carbonates via the cycloaddition of CO2 to epoxides is a standard methodology for CO2 fixation.For this purpose,chiral basket-handle porphyrin-Co complexes were devised,prepared,and fully characterized by nuclear magnetic resonance,mass spectrometry,Fourier transform infrared spectroscopy,ultraviolet-visible spectroscopy,and specific rotation.The proposed metalloporphyrin catalysts were synthesized with either 1,1'-bi-2-naphthol or L-phenylalanine,which have different chirality,and then applied to the coupling of propylene oxide and CO2 for generating chiral cyclic carbonates with good enantioselectivity under extremely mild conditions in the presence of tetrabutyl ammonium chloride as a co-catalyst.The good enantioselectivity in the cycloaddition reaction is attributed to a synergistic interplay between the chiral porphyrin catalysts and the substrate.The mechanism and enantioselectivity of the asymmetric cycloaddition reaction is discussed.
基金supported by the National Natural Science Foundation of China(41330317,21403051)the Natural Science Foundation of Hebei province(B2016402030,B2017402079)+2 种基金the Science and Technology Foundation of Universities of Hebei Province(ZD2015113)the Science and Technology Research Development Program of Handan(1621211041-3,1622201049-2)the Program for One Hundred Innovative Talents in Universities of Hebei Province(BR2-204)~~
文摘A series of zwitterionic‐type quaternary ammoniums(ZTQAs)with varying lengths of alkyl chains combined with KI were synthesized and considered as catalysts for the coupling reaction of CO2 and various terminal epoxides.The prolonged alkyl chain of ZTQAs exhibited temperature‐responsive self‐separation in propylene carbonate(PC).The interaction between ZTQAs and KI was confirmed by X‐ray photoelectron spectroscopy and quantum chemical calculations.This interaction strengthened the nucleophilicity of the I?ion,favoring the catalytic reaction.The 3‐(dimethyltetradecylammonium)propane sulfonate(DTPS)/KI showed an excellent yield of PC(95.1%)at 125°C,1.5 MPa,and 1 mol%loading of catalyst.The precipitate formed spontaneously from the catalytic system,providing high catalytic activity of the homogeneous catalyst,as well as easy recovery of the heterogeneous catalyst.
