In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects o...In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.展开更多
A series of chiral secondary alcohols were easily prepared by means of asymmetric hydrogenation of prochiral aromatic ketones using a new（（Rax）-BuP）/（R,R）-DPEN-Ru（Ⅱ） complex catalyst system.The hydrogenation ...A series of chiral secondary alcohols were easily prepared by means of asymmetric hydrogenation of prochiral aromatic ketones using a new（（Rax）-BuP）/（R,R）-DPEN-Ru（Ⅱ） complex catalyst system.The hydrogenation of 2-methylacetophenone in n-butanol （t-BuOK/Ru =45.6/1,S/C = 500,20 atm.of H2,20℃,48 h） afforded（S）-1-（2＇-methylphenyl）ethanol in 92%ee and〉99% conversion.展开更多
Novel chiral PN_4-type multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis（o-formylphenyl）phenylphosphane and various chiral amino-sulfonamides.Their structures ...Novel chiral PN_4-type multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis（o-formylphenyl）phenylphosphane and various chiral amino-sulfonamides.Their structures were fully characterized by IR,EI-MS and NMR.The catalytic systems,prepared in situ from the multidentate ligands and iridium（I） complexes,showed high activity in asymmetric transfer hydrogenation of propiophenone in 2-propanol solution,leading to corresponding optical alcohol with up to 75%ee.展开更多
Polydentate ligands, N,N’-bis[o-(diphenylphosphino)benzylidene]-1,2-propane-dia-mine [P2N2Me for short] and N,N’-bis[o-(diphenylphosphino)benzy1]-12-propanediamine [P2N2 H4Me for short] have been synthesized. The in...Polydentate ligands, N,N’-bis[o-(diphenylphosphino)benzylidene]-1,2-propane-dia-mine [P2N2Me for short] and N,N’-bis[o-(diphenylphosphino)benzy1]-12-propanediamine [P2N2 H4Me for short] have been synthesized. The interaction of RuCl2(DMSO)4 with one equiv-alent of P2N2Me or P2N2H4Me in refluxing toluene gave trans-RuCl2(P2N2Me) and trans-RuClz(P2N4H4Me) in good yield, respectively. The ligands and the complexes have been fully characterized by elemental analysis and spectroscopic methods. The complexes act as an excellent catalyst precursor in hydrogen transfer hydrogenation of aretophenone in catalyst: aretophenone :iso-PrOK of 1: 100: 15, leading to 2-phenylethanol of 89-96% yield.展开更多
基金the NSFC(No.20272037),the Doctor's Foundation of Education Ministry of China(No.20030610022)Foundation of Xihua University(No.R0723315) and(No.07ZA109) for the financial support of this work.
文摘In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.
基金the National Natural Science Foundation of China(Nos.20343005,20473107,20673130,and 20773147)the Hong Kong PolyU Joint Supervision Scheme(A-PH78) for financial support.
文摘A series of chiral secondary alcohols were easily prepared by means of asymmetric hydrogenation of prochiral aromatic ketones using a new（（Rax）-BuP）/（R,R）-DPEN-Ru（Ⅱ） complex catalyst system.The hydrogenation of 2-methylacetophenone in n-butanol （t-BuOK/Ru =45.6/1,S/C = 500,20 atm.of H2,20℃,48 h） afforded（S）-1-（2＇-methylphenyl）ethanol in 92%ee and〉99% conversion.
基金the National Natural Science Foundation of China(Nos20423002 and 20703034)Natural Science Foundation of Fujian Province of China(No2008J0235) for the financial support of this work
文摘Novel chiral PN_4-type multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis（o-formylphenyl）phenylphosphane and various chiral amino-sulfonamides.Their structures were fully characterized by IR,EI-MS and NMR.The catalytic systems,prepared in situ from the multidentate ligands and iridium（I） complexes,showed high activity in asymmetric transfer hydrogenation of propiophenone in 2-propanol solution,leading to corresponding optical alcohol with up to 75%ee.
文摘Polydentate ligands, N,N’-bis[o-(diphenylphosphino)benzylidene]-1,2-propane-dia-mine [P2N2Me for short] and N,N’-bis[o-(diphenylphosphino)benzy1]-12-propanediamine [P2N2 H4Me for short] have been synthesized. The interaction of RuCl2(DMSO)4 with one equiv-alent of P2N2Me or P2N2H4Me in refluxing toluene gave trans-RuCl2(P2N2Me) and trans-RuClz(P2N4H4Me) in good yield, respectively. The ligands and the complexes have been fully characterized by elemental analysis and spectroscopic methods. The complexes act as an excellent catalyst precursor in hydrogen transfer hydrogenation of aretophenone in catalyst: aretophenone :iso-PrOK of 1: 100: 15, leading to 2-phenylethanol of 89-96% yield.
