The efficient catalytic systems generated in situ from RuCl2（PPh3）3 and chiral ligands N,N-bis[2-（di-o-tolylphosphino）-benzyl]cyclohexane-1,2-diamine（2） were employed for asymmetric transfer hydrogenation of aro...The efficient catalytic systems generated in situ from RuCl2（PPh3）3 and chiral ligands N,N-bis[2-（di-o-tolylphosphino）-benzyl]cyclohexane-1,2-diamine（2） were employed for asymmetric transfer hydrogenation of aromatic ketones, giving the corresponding optically active alcohols with high activities（up to 99% conversion） and excellent enantioselectivities（up to 96% e.e.） under mild conditions. The chiral ruthenium（Ⅱ） complex （R,R）-3 has been prepared and characterized by NMR and X-ray crystallography.展开更多
A new chiral β-diketone Cu (Ⅱ) catalyst was synthesized and used for the asymmetric cyclopropanation of styrene with diazoester. A high optical yield (~90%) was achieved. The effect of the structure of substrate on ...A new chiral β-diketone Cu (Ⅱ) catalyst was synthesized and used for the asymmetric cyclopropanation of styrene with diazoester. A high optical yield (~90%) was achieved. The effect of the structure of substrate on the enantioselectivity was studied. Both chendcal yield and optical yield being reduced when the steric bulky substrate was employed. The reaction mechanism and the chiral model of the transition state are under fufther investigation.展开更多
Using DFT/TDDFT methods,the excited-state lifetimes of Ru（Ⅱ） polypyridyl complexes were computed accurately and the reason of Ru（Ⅱ） polypyridyl complexes with long excited-state lifetimes was explained by the el...Using DFT/TDDFT methods,the excited-state lifetimes of Ru（Ⅱ） polypyridyl complexes were computed accurately and the reason of Ru（Ⅱ） polypyridyl complexes with long excited-state lifetimes was explained by the electron-transfer distances and HOMO-LUMO gaps.Finally,the photovoltaic conversion efficiencies of complexes were predicted using DFT and docking methods.This work has provided methods of predicting the excited-state lifetimes and photovoltaic conversion efficiencies of Ru（Ⅱ） polypyridyl complexes.展开更多
Antidepressant duloxetine （1） was prepared via asymmetric transfer hydrogenation of 3-（dimethylamino）-1-（thiophen-2- yl）propan-1-one （3）. The Ru（Ⅱ）, Rh（Ⅲ） and Ir（Ⅲ） complexes of several chiral ligands...Antidepressant duloxetine （1） was prepared via asymmetric transfer hydrogenation of 3-（dimethylamino）-1-（thiophen-2- yl）propan-1-one （3）. The Ru（Ⅱ）, Rh（Ⅲ） and Ir（Ⅲ） complexes of several chiral ligands were examined as the catalyst and （S,S）-N-tosyl-1,2-diphenyl ethylenediamine （TsDPEN）-Ru（Ⅱ） complex was found to provide good yield and excellent enantioselectivity. 2007 Ming Yan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
The interactions of mixed porphyrin-polypyridyl Ru（Ⅱ） complexes [m（Py-3＇）TPP-Ru（phen）2Cl]^＋（1） and its derivatives [Nim（Py-3＇）TPP-Ru（phen）2Cl]＋（2） and [Cum（Py-3＇）TPP-Ru（phen）2Cl]^＋（3）（phen=...The interactions of mixed porphyrin-polypyridyl Ru（Ⅱ） complexes [m（Py-3＇）TPP-Ru（phen）2Cl]^＋（1） and its derivatives [Nim（Py-3＇）TPP-Ru（phen）2Cl]＋（2） and [Cum（Py-3＇）TPP-Ru（phen）2Cl]^＋（3）（phen=1,10-phenanthroline; m（Py-3＇）TPP=5-（3＇-pyridyl）-10,15,20-triphenylporphyrin） with bovine serum albumin（BSA） were investigated by fluorescence, UV-Vis and circular dichroism（CD） spectroscopies. The UV-Vis and CD spectral experiments indicated that the secondary structures of the protein were perturbed in the presence of the porphyrin Ru（Ⅱ） complex and the perturbation was enhanced under the irradiation with ultra-violet light. The fluorescence quenching mechanism of BSA by the three complexes was determined to be a static process, and the apparent binding constant K values for complexes 1, 2 and 3 measured by fluorescence quenching method were （3.86±0.03）×10^3 L/mol（n=0.94±0.04）, （5.69±0.04）× 103 L/mol（n=1.03±0.06）, and （6.54±0.02）× 10^3 L/mol（n=1.03±0.05）, respectively.展开更多
Twelve chiral copper(Ⅱ) Schiff base complexes, derived from (R) (+) 2 amino 1,1 diaryl 1 propanol with substituted salicylaldehydes, were examined as a catalyst for asymmetric cyclopropanation of styrene with ethyl d...Twelve chiral copper(Ⅱ) Schiff base complexes, derived from (R) (+) 2 amino 1,1 diaryl 1 propanol with substituted salicylaldehydes, were examined as a catalyst for asymmetric cyclopropanation of styrene with ethyl diazoacetate. It was found that the substituents at 3 and 5 positions of salicylaldehyde in the ligands had great effects on catalytic activity and enantioselectivity of the catalyst. The complex with strong electron withdrawing group (NO 2) at 5 position and the smallest stereo hinder (H) at 3 position of salicylaldehyde showed highly catalytic activity and enantioselectivity, up to ee =87 4% for trans and ee =82 8% for cis isomers respectively, and the ratio 39/61 of cis to trans isomers was obtained at 40 ℃ with 1,2 dichloroethane as solvent.展开更多
基金Supported by the National Natural Science Foundation of China(Nos.2042300220703034)+1 种基金the Natural Science Foundation of Fujian Province of China(No.2008J0235)the Natural Science Foundation of Guangxi Province of China(No. 0991016)
文摘The efficient catalytic systems generated in situ from RuCl2（PPh3）3 and chiral ligands N,N-bis[2-（di-o-tolylphosphino）-benzyl]cyclohexane-1,2-diamine（2） were employed for asymmetric transfer hydrogenation of aromatic ketones, giving the corresponding optically active alcohols with high activities（up to 99% conversion） and excellent enantioselectivities（up to 96% e.e.） under mild conditions. The chiral ruthenium（Ⅱ） complex （R,R）-3 has been prepared and characterized by NMR and X-ray crystallography.
文摘A new chiral β-diketone Cu (Ⅱ) catalyst was synthesized and used for the asymmetric cyclopropanation of styrene with diazoester. A high optical yield (~90%) was achieved. The effect of the structure of substrate on the enantioselectivity was studied. Both chendcal yield and optical yield being reduced when the steric bulky substrate was employed. The reaction mechanism and the chiral model of the transition state are under fufther investigation.
基金Supported by the State Key Program of Fundamental Research( G19980 613 0 8) National Natural Science Foundationof China( Nos.2 99710 0 5 ,2 0 0 2 3 0 0 5 ,2 0 0 710 0 4) ,and Scientific Research Foundation for the Returned Overseas ChineseScholars( State
基金supported by the Research Foundation of the National Natural Science Foundation of China(No.U1204209)the Major Program of the Natural Science of Anhui University(No.KJ2016SD52)+1 种基金the Key Program of the Natural Science of Anhui University for Young and Middle-aged Key Talent to Study in the Domestic(No.gxfx ZD2016097)Undergraduates Innovating Project(No.201510373083)
文摘Using DFT/TDDFT methods,the excited-state lifetimes of Ru（Ⅱ） polypyridyl complexes were computed accurately and the reason of Ru（Ⅱ） polypyridyl complexes with long excited-state lifetimes was explained by the electron-transfer distances and HOMO-LUMO gaps.Finally,the photovoltaic conversion efficiencies of complexes were predicted using DFT and docking methods.This work has provided methods of predicting the excited-state lifetimes and photovoltaic conversion efficiencies of Ru（Ⅱ） polypyridyl complexes.
基金We thank the National Natural Science Foundation of China （No. 20472061）；Guangzhou Bureau of Science and Technology for financial support of this study.
文摘Antidepressant duloxetine （1） was prepared via asymmetric transfer hydrogenation of 3-（dimethylamino）-1-（thiophen-2- yl）propan-1-one （3）. The Ru（Ⅱ）, Rh（Ⅲ） and Ir（Ⅲ） complexes of several chiral ligands were examined as the catalyst and （S,S）-N-tosyl-1,2-diphenyl ethylenediamine （TsDPEN）-Ru（Ⅱ） complex was found to provide good yield and excellent enantioselectivity. 2007 Ming Yan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
基金Supported by the National Natural Science Foundation of China(Nos.20871056, 20771044 and 20901030)the Natural Science Foundation of Guangdong Province, China(Nos.8251063201000008 and 9451063201002077)+1 种基金the Planned Item of Science and Technology of Guangdong Province, China (No.2008A030201020)the "211" Project Grant of Jinan University,China
文摘The interactions of mixed porphyrin-polypyridyl Ru（Ⅱ） complexes [m（Py-3＇）TPP-Ru（phen）2Cl]^＋（1） and its derivatives [Nim（Py-3＇）TPP-Ru（phen）2Cl]＋（2） and [Cum（Py-3＇）TPP-Ru（phen）2Cl]^＋（3）（phen=1,10-phenanthroline; m（Py-3＇）TPP=5-（3＇-pyridyl）-10,15,20-triphenylporphyrin） with bovine serum albumin（BSA） were investigated by fluorescence, UV-Vis and circular dichroism（CD） spectroscopies. The UV-Vis and CD spectral experiments indicated that the secondary structures of the protein were perturbed in the presence of the porphyrin Ru（Ⅱ） complex and the perturbation was enhanced under the irradiation with ultra-violet light. The fluorescence quenching mechanism of BSA by the three complexes was determined to be a static process, and the apparent binding constant K values for complexes 1, 2 and 3 measured by fluorescence quenching method were （3.86±0.03）×10^3 L/mol（n=0.94±0.04）, （5.69±0.04）× 103 L/mol（n=1.03±0.06）, and （6.54±0.02）× 10^3 L/mol（n=1.03±0.05）, respectively.
文摘Twelve chiral copper(Ⅱ) Schiff base complexes, derived from (R) (+) 2 amino 1,1 diaryl 1 propanol with substituted salicylaldehydes, were examined as a catalyst for asymmetric cyclopropanation of styrene with ethyl diazoacetate. It was found that the substituents at 3 and 5 positions of salicylaldehyde in the ligands had great effects on catalytic activity and enantioselectivity of the catalyst. The complex with strong electron withdrawing group (NO 2) at 5 position and the smallest stereo hinder (H) at 3 position of salicylaldehyde showed highly catalytic activity and enantioselectivity, up to ee =87 4% for trans and ee =82 8% for cis isomers respectively, and the ratio 39/61 of cis to trans isomers was obtained at 40 ℃ with 1,2 dichloroethane as solvent.
