A new chiral monomer,(S)‐5,5′‐divinyl‐BINAP,was successfully synthesized and embedded intotwo different porous organic polymers(Poly‐1and Poly‐2).After loading a Rh species,the catalystswere applied for the hete...A new chiral monomer,(S)‐5,5′‐divinyl‐BINAP,was successfully synthesized and embedded intotwo different porous organic polymers(Poly‐1and Poly‐2).After loading a Rh species,the catalystswere applied for the heterogeneous asymmetric hydroformylation of styrene.Compared with thehomogeneous BINAP analogue,the enantioselectivity of Rh/Poly‐1catalyst was drastically increasedby approximately70%.The improved enantioselectivity of the porous Rh/BINAP polymerswas attributed to the presence of flexible chiral nanopockets resulting from the increased bulk ofthe R groups near the catalytic center.展开更多
Two vinyl‐functionalized chiral2,2'‐bis(diphenylphosphino)‐1,1'‐binaphthyl(BINAP)ligands,(S)‐4,4'‐divinyl‐BINAP and(S)‐5,5'‐divinyl‐BINAP,were successfully synthesized.Chiral BINAP‐based por...Two vinyl‐functionalized chiral2,2'‐bis(diphenylphosphino)‐1,1'‐binaphthyl(BINAP)ligands,(S)‐4,4'‐divinyl‐BINAP and(S)‐5,5'‐divinyl‐BINAP,were successfully synthesized.Chiral BINAP‐based porous organic polymers(POPs),denoted as4‐BINAP@POPs and5‐BINAP@POPs,were efficiently prepared via the copolymerization of vinyl‐functionalized BINAP with divinyl benzene under solvothermal conditions.Thorough characterization using nuclear magnetic resonance spectroscopy,thermogravimetric analysis,extended X‐ray absorption fine structure analysis,and high‐angle annular dark‐field scanning transmission electron microscopy,we confirmed that chiral BINAP groups were successfully incorporated into the structure of the materials considered to contain hierarchical pores.Ru was introduced as a catalytic species into the POPs using different synthetic routes.Systematic investigation of the resultant chiral Ru/POP catalysts for heterogeneous asymmetric hydrogenation ofβ‐keto esters revealed their excellent chiral inducibility as well as high activity and stability.Our work thereby paves a path towards the use of advanced hierarchical porous polymers as solid chiral platforms for heterogeneous asymmetric catalysis.展开更多
基金supported by the Strategic priority Research Program of the Chinese Academy of Sciences (XDB17020400)~~
文摘A new chiral monomer,(S)‐5,5′‐divinyl‐BINAP,was successfully synthesized and embedded intotwo different porous organic polymers(Poly‐1and Poly‐2).After loading a Rh species,the catalystswere applied for the heterogeneous asymmetric hydroformylation of styrene.Compared with thehomogeneous BINAP analogue,the enantioselectivity of Rh/Poly‐1catalyst was drastically increasedby approximately70%.The improved enantioselectivity of the porous Rh/BINAP polymerswas attributed to the presence of flexible chiral nanopockets resulting from the increased bulk ofthe R groups near the catalytic center.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020400)~~
文摘Two vinyl‐functionalized chiral2,2'‐bis(diphenylphosphino)‐1,1'‐binaphthyl(BINAP)ligands,(S)‐4,4'‐divinyl‐BINAP and(S)‐5,5'‐divinyl‐BINAP,were successfully synthesized.Chiral BINAP‐based porous organic polymers(POPs),denoted as4‐BINAP@POPs and5‐BINAP@POPs,were efficiently prepared via the copolymerization of vinyl‐functionalized BINAP with divinyl benzene under solvothermal conditions.Thorough characterization using nuclear magnetic resonance spectroscopy,thermogravimetric analysis,extended X‐ray absorption fine structure analysis,and high‐angle annular dark‐field scanning transmission electron microscopy,we confirmed that chiral BINAP groups were successfully incorporated into the structure of the materials considered to contain hierarchical pores.Ru was introduced as a catalytic species into the POPs using different synthetic routes.Systematic investigation of the resultant chiral Ru/POP catalysts for heterogeneous asymmetric hydrogenation ofβ‐keto esters revealed their excellent chiral inducibility as well as high activity and stability.Our work thereby paves a path towards the use of advanced hierarchical porous polymers as solid chiral platforms for heterogeneous asymmetric catalysis.
