By virtue of the atom-and step-economy, utilization of simple arenes as a supplant of pre-prepared aryl metal species or aryl halides for the synthesis of arylated chiral molecules has attracted great attention from t...By virtue of the atom-and step-economy, utilization of simple arenes as a supplant of pre-prepared aryl metal species or aryl halides for the synthesis of arylated chiral molecules has attracted great attention from the synthetic community. While transition-metal-catalyzed enantioselective diarylation of tethered alkenes has been employed to prepare important chiral cyclic compounds, the direct use of simple arenes as aryl precursors is still underdeveloped, probably due to the difficulties in the effective control of the reactivity, site-selectivity and/or enantioselectivity. Herein we report an asymmetric Pd/Ag dual metal catalytic system for the non-directed, site-and enantioselective domino Heck/intermolecular C–H functionalization of arenes.Mechanistic studies showed that Pd and Ag act in cooperation in the catalysis and the chiral bisphosphine ligand plays a bifunctional role, i.e., assisting the silver species in the cleavage of the aryl C–H bond, while inducing the enantioselectivity on direct complexation with palladium. This method provides an efficient approach to the corresponding chiral oxindoles with good enantiomeric excesses from a broad scope of arenes, including fluoroarenes, heteroarenes and several complex products derived from medicines or natural products.展开更多
This paper reports a stable heterogeneous nanoparticles catalyst MnFe2O4@PANI@Ag for the degradation of azo dyes. In this synthesizing method, MnFe204 is used as magnetic core and polyaniline (PANI) a linker to stab...This paper reports a stable heterogeneous nanoparticles catalyst MnFe2O4@PANI@Ag for the degradation of azo dyes. In this synthesizing method, MnFe204 is used as magnetic core and polyaniline (PANI) a linker to stabilize the Ag nanoparticles (NPs) on the surface of catalyst. The method has a high ability to prevent Ag NPs from aggregation on the PANI surface, thus resulting in small size and highly dispersed Ag NPs. The composition and nano-structural features of polycrystalline sample were studied by X-ray powder diffractometry, Fourier transform infrared spectroscopy, and scanning electron microsco- py. Vibrating sample magnetometer measurements proved the super-paramagnetic property of the catalyst, and UV results demonstrated that MnFe2O4@PANI@Ag has a high ability to reduce the azo dyes, which come from industrial wastes in the form of pollutant. The nanocomposites could be readily separated by magnet and reused for the next four reductions with high generation efficiency.展开更多
基金supported by the National Key R&D Program of China (2021YFA1500100)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0610000)+2 种基金the National Natural Science Foundation of China (92256303, 22171278, 21821002)the Shanghai Science and Technology Committee (23ZR1482400)the Natural Science Foundation of Ningbo (2023J034)。
文摘By virtue of the atom-and step-economy, utilization of simple arenes as a supplant of pre-prepared aryl metal species or aryl halides for the synthesis of arylated chiral molecules has attracted great attention from the synthetic community. While transition-metal-catalyzed enantioselective diarylation of tethered alkenes has been employed to prepare important chiral cyclic compounds, the direct use of simple arenes as aryl precursors is still underdeveloped, probably due to the difficulties in the effective control of the reactivity, site-selectivity and/or enantioselectivity. Herein we report an asymmetric Pd/Ag dual metal catalytic system for the non-directed, site-and enantioselective domino Heck/intermolecular C–H functionalization of arenes.Mechanistic studies showed that Pd and Ag act in cooperation in the catalysis and the chiral bisphosphine ligand plays a bifunctional role, i.e., assisting the silver species in the cleavage of the aryl C–H bond, while inducing the enantioselectivity on direct complexation with palladium. This method provides an efficient approach to the corresponding chiral oxindoles with good enantiomeric excesses from a broad scope of arenes, including fluoroarenes, heteroarenes and several complex products derived from medicines or natural products.
基金supported by Fatih University under BAP(Grant No:P50021301-Y(3146)
文摘This paper reports a stable heterogeneous nanoparticles catalyst MnFe2O4@PANI@Ag for the degradation of azo dyes. In this synthesizing method, MnFe204 is used as magnetic core and polyaniline (PANI) a linker to stabilize the Ag nanoparticles (NPs) on the surface of catalyst. The method has a high ability to prevent Ag NPs from aggregation on the PANI surface, thus resulting in small size and highly dispersed Ag NPs. The composition and nano-structural features of polycrystalline sample were studied by X-ray powder diffractometry, Fourier transform infrared spectroscopy, and scanning electron microsco- py. Vibrating sample magnetometer measurements proved the super-paramagnetic property of the catalyst, and UV results demonstrated that MnFe2O4@PANI@Ag has a high ability to reduce the azo dyes, which come from industrial wastes in the form of pollutant. The nanocomposites could be readily separated by magnet and reused for the next four reductions with high generation efficiency.