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
The complex [（CF3-BINAP（O））Rh（COD）][ClO4]·Et2O （2, CFa-BINAP（O） = 2- {bis[3,5-bis（trifluoromethyl）phenyl]phosphino } -2 ＇- {bis [3,5-bis（trifluoromethyl）phenyl]phosphinyl } -1,1、-binaphthyl, COD = ...The complex [（CF3-BINAP（O））Rh（COD）][ClO4]·Et2O （2, CFa-BINAP（O） = 2- {bis[3,5-bis（trifluoromethyl）phenyl]phosphino } -2 ＇- {bis [3,5-bis（trifluoromethyl）phenyl]phosphinyl } -1,1、-binaphthyl, COD = 1,5-cyclooctadiene） was obtained directly from the reaction of CF3- BINAP（O） ligand with [Rh（COD）][C104]. Complex 2 has been characterized by single-crystal X-ray diffraction. The crystal adopts space group P21/n with a = 19.0727（4）, b = 15.6275（4）, c = 22.3039（6） A, fl = 112.3570（10）°, V= 6148.2（3） A3, Z = 4, Dc = 1.693 g/cm3, F（000） = 3144, μ（MoKa） = 0.500 mm-1, the final R = 0.0947 and wR = 0.2501. Structural studies reveal that Rh（I） is coordinated by one oxygen and one phosphorus in the same ligand. Asymmetric hydrogenation of acetami- docinnamic acid with compound 2 was also evaluated.展开更多
[（BINAP）Pt（C≡CC6H4R-p）2] （R = H, 1; CH3, 2） （BINAP = 2,2＇-bis（diphenylphosphino）-1,1＇-binaphthyl） were synthesized and characterized by X-ray crystallography. Complex 1 crystallizes in triclinic, space gr...[（BINAP）Pt（C≡CC6H4R-p）2] （R = H, 1; CH3, 2） （BINAP = 2,2＇-bis（diphenylphosphino）-1,1＇-binaphthyl） were synthesized and characterized by X-ray crystallography. Complex 1 crystallizes in triclinic, space group P1^- with a = 11.699（3）, b = 12.512（3）, c = 15.611（4） ,A^°, α= 93.277（3）, β= 97.626（2）, γ = 97.375（14）°, V = 2239.9（9） ,A^°3, Mr = 1014.92, Z = 2, Dc = 1.505 g/cm^3, F（000） = 1010,μ（MoKα） = 3.244 mm^-1, the final R = 0.0338 and wR = 0.0905 for 7738 observed reflections （1 〉 2σ（I））. Complex 2 crystallizes in monoclinic, space group P2（1/n） with a = 18.03690 （10）, b = 13.06060（10）, c = 21.6913（3） A^°,β= 96.5430（10）°, V= 5076.60（9） A^3, Mr = 1132.94, Z = 4, Dc = 1.482 g/cm^3, F（000） = 2272,μ（MoKα） = 2.973 mm^-1, the final R = 0.0481 and wR = 0.0893 for 8916 observed reflections （1 〉 2σ（I））. Both complexes emit intensively photoluminescence in both solid state and fluid solution due to MLCT （Pt→C≡CC6H4R-p） emissive state.展开更多
Enantioselective liquid–liquid extraction has attracted considerable attention for its potential use in largescale production. Kinetic data are needed for the reliable scale-up of the process. This paper reports the ...Enantioselective liquid–liquid extraction has attracted considerable attention for its potential use in largescale production. Kinetic data are needed for the reliable scale-up of the process. This paper reports the kinetic study of reactive extraction of phenylalanine(Phe) enantiomers with BINAP–copper complex(BINAP–Cu) as a chiral selector. The theory of extraction accompanied by a chemical reaction was applied.The effects of agitation speed, interfacial area, p H value of aqueous phase, initial concentration of Phe enantiomers and initial concentration of BINAP–Cu on the specific rate of extraction were investigated. The forward rate constants of the reactions in the reactive extraction process are 7.93 × 10-5m5/2·mol-1/2·s-1for D-Phe and 1.29 × 10-4m5/2·mol-1/2·s-1for L-Phe.展开更多
5,5-Diamino BINAP has been synthesized via three steps using BINAPO as starting material with high reaction yield. Present method needed only a stoichiometric quantity of nitric acid in the step of nitration of BINAPO...5,5-Diamino BINAP has been synthesized via three steps using BINAPO as starting material with high reaction yield. Present method needed only a stoichiometric quantity of nitric acid in the step of nitration of BINAPO, giving almost quantitative reaction yield. Based on 5,5-diamino BINAP, other three new BINAP derivatives have been synthesized. These modified BINAP ligands showed better catalytic properties as compared to BINAP itself in the asymmetric hydrogenation of 2-(6'-methoxyl-2'-naphthyl)acrylic acid.展开更多
A new type of chiral dendritic ligands with 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) located at the focal point of the dendrimer has been synthesized through the condensation reaction of 5-amino BINAP and...A new type of chiral dendritic ligands with 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) located at the focal point of the dendrimer has been synthesized through the condensation reaction of 5-amino BINAP and Fréchet-type poly (aryl ether) dendrons with carboxyl groups as the linker in high reaction yields, respectively. The ruthenium complexes of these dendritic ligands were found to be very efficient catalysts in asymmetric hydrogenation of 2-phenylacryclic acids as well as facile catalyst recycling.展开更多
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.
基金Supported by the National Natural Science Foundation of China(20972159)
文摘The complex [（CF3-BINAP（O））Rh（COD）][ClO4]·Et2O （2, CFa-BINAP（O） = 2- {bis[3,5-bis（trifluoromethyl）phenyl]phosphino } -2 ＇- {bis [3,5-bis（trifluoromethyl）phenyl]phosphinyl } -1,1、-binaphthyl, COD = 1,5-cyclooctadiene） was obtained directly from the reaction of CF3- BINAP（O） ligand with [Rh（COD）][C104]. Complex 2 has been characterized by single-crystal X-ray diffraction. The crystal adopts space group P21/n with a = 19.0727（4）, b = 15.6275（4）, c = 22.3039（6） A, fl = 112.3570（10）°, V= 6148.2（3） A3, Z = 4, Dc = 1.693 g/cm3, F（000） = 3144, μ（MoKa） = 0.500 mm-1, the final R = 0.0947 and wR = 0.2501. Structural studies reveal that Rh（I） is coordinated by one oxygen and one phosphorus in the same ligand. Asymmetric hydrogenation of acetami- docinnamic acid with compound 2 was also evaluated.
基金This work was supported by NSF of Fujian Province (E0420002 and E0310029)
文摘[（BINAP）Pt（C≡CC6H4R-p）2] （R = H, 1; CH3, 2） （BINAP = 2,2＇-bis（diphenylphosphino）-1,1＇-binaphthyl） were synthesized and characterized by X-ray crystallography. Complex 1 crystallizes in triclinic, space group P1^- with a = 11.699（3）, b = 12.512（3）, c = 15.611（4） ,A^°, α= 93.277（3）, β= 97.626（2）, γ = 97.375（14）°, V = 2239.9（9） ,A^°3, Mr = 1014.92, Z = 2, Dc = 1.505 g/cm^3, F（000） = 1010,μ（MoKα） = 3.244 mm^-1, the final R = 0.0338 and wR = 0.0905 for 7738 observed reflections （1 〉 2σ（I））. Complex 2 crystallizes in monoclinic, space group P2（1/n） with a = 18.03690 （10）, b = 13.06060（10）, c = 21.6913（3） A^°,β= 96.5430（10）°, V= 5076.60（9） A^3, Mr = 1132.94, Z = 4, Dc = 1.482 g/cm^3, F（000） = 2272,μ（MoKα） = 2.973 mm^-1, the final R = 0.0481 and wR = 0.0893 for 8916 observed reflections （1 〉 2σ（I））. Both complexes emit intensively photoluminescence in both solid state and fluid solution due to MLCT （Pt→C≡CC6H4R-p） emissive state.
基金Supported by the National Natural Science Foundation of China(21171054)the Open Fund Project of Key Laboratory in Hunan University(11K029)the Key Laboratory of Hunan Province and Aid program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province
文摘Enantioselective liquid–liquid extraction has attracted considerable attention for its potential use in largescale production. Kinetic data are needed for the reliable scale-up of the process. This paper reports the kinetic study of reactive extraction of phenylalanine(Phe) enantiomers with BINAP–copper complex(BINAP–Cu) as a chiral selector. The theory of extraction accompanied by a chemical reaction was applied.The effects of agitation speed, interfacial area, p H value of aqueous phase, initial concentration of Phe enantiomers and initial concentration of BINAP–Cu on the specific rate of extraction were investigated. The forward rate constants of the reactions in the reactive extraction process are 7.93 × 10-5m5/2·mol-1/2·s-1for D-Phe and 1.29 × 10-4m5/2·mol-1/2·s-1for L-Phe.
基金the National Natural Science Foundation of China (Nos. 20325209 and 20132010) and Chinese Academy of Sciences.
文摘5,5-Diamino BINAP has been synthesized via three steps using BINAPO as starting material with high reaction yield. Present method needed only a stoichiometric quantity of nitric acid in the step of nitration of BINAPO, giving almost quantitative reaction yield. Based on 5,5-diamino BINAP, other three new BINAP derivatives have been synthesized. These modified BINAP ligands showed better catalytic properties as compared to BINAP itself in the asymmetric hydrogenation of 2-(6'-methoxyl-2'-naphthyl)acrylic acid.
文摘A new type of chiral dendritic ligands with 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) located at the focal point of the dendrimer has been synthesized through the condensation reaction of 5-amino BINAP and Fréchet-type poly (aryl ether) dendrons with carboxyl groups as the linker in high reaction yields, respectively. The ruthenium complexes of these dendritic ligands were found to be very efficient catalysts in asymmetric hydrogenation of 2-phenylacryclic acids as well as facile catalyst recycling.
