A C2-symmetrical aryl diphosphite derived from chiral binaphthol was prepared and its rhodium complex was used as catalysts in the asymmetric hydroformylation of olefins. High catalytic activity and good regioselectiv...A C2-symmetrical aryl diphosphite derived from chiral binaphthol was prepared and its rhodium complex was used as catalysts in the asymmetric hydroformylation of olefins. High catalytic activity and good regioselectivity were observed. Up to 31.2% ee and 38.1% ee were achieved for the hydroformylation of 4-fluoro-styrene and vinyl acetate respectively. The influences of ligand-to-metal ratio, reaction temperature and the pressure of syn-gas on the enantioselectivity and regioselectivity were also studied.展开更多
The title complex,6,6-（3,3,5,5-tetra-tert-butylbiphenyl-2,2-diyl）bis（oxy）di-di-benzo[d,f]-[1,3,2] dioxaphosphepine（C52H56O6P2·C6H14,Mr = 881.99）,was synthesized,and the structure was determined by X-ray sin...The title complex,6,6-（3,3,5,5-tetra-tert-butylbiphenyl-2,2-diyl）bis（oxy）di-di-benzo[d,f]-[1,3,2] dioxaphosphepine（C52H56O6P2·C6H14,Mr = 881.99）,was synthesized,and the structure was determined by X-ray single-crystal diffraction.The crystal belongs to the orthor-hombic system,space group Pbca,with a = 11.8400（13）,b = 25.381（3）,c = 34.243（4） ,V = 10290（2）（A°）^3,Z = 8,Dc = 1.139 g/cm^3,μ = 0.131 mm^-1,T = 152（2） K,F（000） = 3768,the final R = 0.0773 and wR = 0.1820 for 9721 observed reflections with I 〉 2σ（I）.The neighboring two molecules form a dimmer by face-to-face π…π interactions.展开更多
Chiral diphosphite ligands were prepared by the reaction of (1R,5S,6R)-(trans,trans)-spiro[4.4]nonane-1,6-diol with chlorophosphites. The rhodium(I) complexes containing these ligands were tested in the asymmetric hyd...Chiral diphosphite ligands were prepared by the reaction of (1R,5S,6R)-(trans,trans)-spiro[4.4]nonane-1,6-diol with chlorophosphites. The rhodium(I) complexes containing these ligands were tested in the asymmetric hydro-formylation of styrene and moderate enantioselectivity (up to 49% ee) was obtained. A pair of diastereomers 5a and 5b gave the opposite configuration of the product, which implies that the sense of enantioface selection is mainly dictated by the configuration of the terminal group on the ligand.展开更多
基金Project supported by the Suzhou University and the Hong Kong Polytechnic University ASD Fund and University Grants Committee Area of Excel-lence Scheme in Hong Kong (AoE P/10-01).
文摘A C2-symmetrical aryl diphosphite derived from chiral binaphthol was prepared and its rhodium complex was used as catalysts in the asymmetric hydroformylation of olefins. High catalytic activity and good regioselectivity were observed. Up to 31.2% ee and 38.1% ee were achieved for the hydroformylation of 4-fluoro-styrene and vinyl acetate respectively. The influences of ligand-to-metal ratio, reaction temperature and the pressure of syn-gas on the enantioselectivity and regioselectivity were also studied.
基金supported by the SINOPEC project (G6001-2-11ZS0460)
文摘The title complex,6,6-（3,3,5,5-tetra-tert-butylbiphenyl-2,2-diyl）bis（oxy）di-di-benzo[d,f]-[1,3,2] dioxaphosphepine（C52H56O6P2·C6H14,Mr = 881.99）,was synthesized,and the structure was determined by X-ray single-crystal diffraction.The crystal belongs to the orthor-hombic system,space group Pbca,with a = 11.8400（13）,b = 25.381（3）,c = 34.243（4） ,V = 10290（2）（A°）^3,Z = 8,Dc = 1.139 g/cm^3,μ = 0.131 mm^-1,T = 152（2） K,F（000） = 3768,the final R = 0.0773 and wR = 0.1820 for 9721 observed reflections with I 〉 2σ（I）.The neighboring two molecules form a dimmer by face-to-face π…π interactions.
基金Project supported by the National Natural Science Foundation of China (No. 20202009).
文摘Chiral diphosphite ligands were prepared by the reaction of (1R,5S,6R)-(trans,trans)-spiro[4.4]nonane-1,6-diol with chlorophosphites. The rhodium(I) complexes containing these ligands were tested in the asymmetric hydro-formylation of styrene and moderate enantioselectivity (up to 49% ee) was obtained. A pair of diastereomers 5a and 5b gave the opposite configuration of the product, which implies that the sense of enantioface selection is mainly dictated by the configuration of the terminal group on the ligand.
