The asymmetric photocatalytic organic synthesis(APOS)process is a sustainable and environmentally benign method for the production of optically active chemicals with sunlight as an energy source.However,it still lacks...The asymmetric photocatalytic organic synthesis(APOS)process is a sustainable and environmentally benign method for the production of optically active chemicals with sunlight as an energy source.However,it still lacks efficient semiconductors with tunable band structures and has a low recycling stability.Herein,we report the synthesis of tetrahydroquinoline-linked covalent organic frameworks(QH-COFs)with irreversible tetrahydroquinoline linkage as efficient semiconductors for the visible-light-driven asymmetricα-alkylation of aldehydes by merging with a chiral secondary amine.Up to 94%ee was obtained over QH-COFs,and the activity of QH-COFs was significantly higher than those of inorganic semiconductors(e.g.,Ti O2,Bi VO4,and WO3)under similar conditions,which is mainly attributed to their narrow band gap and suitable band edge.As far as we know,QH-COFs are the most active semiconductors for asymmetricα-alkylation of aldehydes ever reported.The QH-COFs were prepared via a one-pot Povarov cascade imine formation and cycloaddition reaction using Sc(OTf)3/Yb(OTf)3 as Lewis acid catalysts.Attributed to the tetrahydroquinoline linkage,QH-COFs showed extremely high recycling stability,which made practicals application possible.This work not only opens up a new avenue for asymmetric photocatalysis but also provides an efficient and general method for the construction of robust COFs.展开更多
As an emerging class of crystalline porous materials, covalent organic frameworks（COFs） have been widely used as catalysts or catalyst supports. Flexible regulation of the pores and easy introduction of functional a...As an emerging class of crystalline porous materials, covalent organic frameworks（COFs） have been widely used as catalysts or catalyst supports. Flexible regulation of the pores and easy introduction of functional active sites onto the skeleton of COFs make them promising platforms for many catalysis applications. However, only a single function is generally observed in these COFs. Herein, we synthesized a negatively charged ionic COF（I-COF） and successfully incorporated functionalized counter ions, that is, metallic Mn2＋ and a coordination complex of manganese（Ⅱ） bipyridine complexes（[Mn（bpy）2]2＋）, via a simple ion exchange process. The resulting I-COFs can act as effective heterogeneous catalysts for epoxidation reactions. We envisage that with this type of ionic architecture, a variety of other functional cations could be exchanged into the frameworks, thus making the COF a versatile platform for different applications.展开更多
文摘The asymmetric photocatalytic organic synthesis(APOS)process is a sustainable and environmentally benign method for the production of optically active chemicals with sunlight as an energy source.However,it still lacks efficient semiconductors with tunable band structures and has a low recycling stability.Herein,we report the synthesis of tetrahydroquinoline-linked covalent organic frameworks(QH-COFs)with irreversible tetrahydroquinoline linkage as efficient semiconductors for the visible-light-driven asymmetricα-alkylation of aldehydes by merging with a chiral secondary amine.Up to 94%ee was obtained over QH-COFs,and the activity of QH-COFs was significantly higher than those of inorganic semiconductors(e.g.,Ti O2,Bi VO4,and WO3)under similar conditions,which is mainly attributed to their narrow band gap and suitable band edge.As far as we know,QH-COFs are the most active semiconductors for asymmetricα-alkylation of aldehydes ever reported.The QH-COFs were prepared via a one-pot Povarov cascade imine formation and cycloaddition reaction using Sc(OTf)3/Yb(OTf)3 as Lewis acid catalysts.Attributed to the tetrahydroquinoline linkage,QH-COFs showed extremely high recycling stability,which made practicals application possible.This work not only opens up a new avenue for asymmetric photocatalysis but also provides an efficient and general method for the construction of robust COFs.
基金supported by the National Natural Science Foundation of China(21473196,21676264)the 100-Talents Program of CASthe State Key Laboratory of Fine Chemicals,Dalian University of Technology(KF1415)~~
文摘As an emerging class of crystalline porous materials, covalent organic frameworks（COFs） have been widely used as catalysts or catalyst supports. Flexible regulation of the pores and easy introduction of functional active sites onto the skeleton of COFs make them promising platforms for many catalysis applications. However, only a single function is generally observed in these COFs. Herein, we synthesized a negatively charged ionic COF（I-COF） and successfully incorporated functionalized counter ions, that is, metallic Mn2＋ and a coordination complex of manganese（Ⅱ） bipyridine complexes（[Mn（bpy）2]2＋）, via a simple ion exchange process. The resulting I-COFs can act as effective heterogeneous catalysts for epoxidation reactions. We envisage that with this type of ionic architecture, a variety of other functional cations could be exchanged into the frameworks, thus making the COF a versatile platform for different applications.
