The full-parameter geometry optimization of cationic （ S ） - BINAP - Ru （ Ⅱ ） halide complex was performed by DFT method using B3LYP, PW91 and PBE potentials with several basis sets. PW91 with 3-21G / SDD basis s...The full-parameter geometry optimization of cationic （ S ） - BINAP - Ru （ Ⅱ ） halide complex was performed by DFT method using B3LYP, PW91 and PBE potentials with several basis sets. PW91 with 3-21G / SDD basis sets is found to be the most suitable method with consideration of both precision and efficiency. The dihedral angles （ θ ） of the binaphthyl or biphenyl with different phosphorus ligand - Ru （ Ⅱ ） halide complexes were found changing from 59.9 to 79.3 degree, while the natural bite angle （ βn ） of those complexes only changes from 87.4 to 90.3 degree. It is different from the common view of asymmetric organic chemists＇ that θ directly influences βn.展开更多
As a structural analog of oxazoline,imidazoline(4,5-dihydroimidazole)has received much attention in the rational design of chiral ligands.The additional N-substituent provides broader space for fine-tuning of electron...As a structural analog of oxazoline,imidazoline(4,5-dihydroimidazole)has received much attention in the rational design of chiral ligands.The additional N-substituent provides broader space for fine-tuning of electronic and steric effects,and it offers a good handle for immobilizing onto solid supports.In the past decades,imidazoline ring has emerged as a powerful candidate for the design of chiral nitrogen-containing ligands,as well as a significant alternative for oxazoline ring.Various chiral imidazoline ligands have been designed and utilized in asymmetric organic reactions.These new catalysts can not only be applied in classical reactions,but also be employed to develop new organic reactions with high enantioselectivities.This review provides an overview of chiral imidazoline ligands.Their applications in asymmetric synthesis are also summarized.展开更多
A series of novel N,O-type chiral ligands derived from enantiopure inherently chiral calix[4]arenes containing quinolin-2-yl-methanol moiety in the cone or partialcone conformation have been synthe-sized and character...A series of novel N,O-type chiral ligands derived from enantiopure inherently chiral calix[4]arenes containing quinolin-2-yl-methanol moiety in the cone or partialcone conformation have been synthe-sized and characterized. Moreover,they have been applied to the catalytic asymmetric addition of diethylzinc to benzaldehyde,which represents the first example that the inherently chiral calixarene can be used as the chiral ligands for the catalytic asymmetric synthesis.展开更多
Chiral ligand (R)-N, N'-Bis(2-hydroxy-3,5-di- tert-butyl-aryl-methyl)-1, 1'-binaphthalene-2,2'-diamine derived from the reduction of Schiff base (R)-2,2'-bis (3,5-di-tert-butyl-2-hy-droxybenzylideneami...Chiral ligand (R)-N, N'-Bis(2-hydroxy-3,5-di- tert-butyl-aryl-methyl)-1, 1'-binaphthalene-2,2'-diamine derived from the reduction of Schiff base (R)-2,2'-bis (3,5-di-tert-butyl-2-hy-droxybenzylideneamino)-1, 1'-binaphthyl with LiAIH(4) is fairly effective in the asymmetric addition reaction of diethylzinc to aldehydes by which good yields (46%-94%) of the corresponding sec-alcohols can be obtained in moderate ee (51%-79%) with R configuration for a variety of aldehydes.展开更多
1 Results The unique structure of chiral ferrocenes allows one to design a variety of chiral phosphine ligands,which are useful tools for metal catalyzed asymmetric reactions.Although some useful chiral ferrocenyl pho...1 Results The unique structure of chiral ferrocenes allows one to design a variety of chiral phosphine ligands,which are useful tools for metal catalyzed asymmetric reactions.Although some useful chiral ferrocenyl phosphine ligands have already been reported,it is still an challenging subject tocreate new ferrocenyl phosphine ligands in order to cover asymmetric reactions in which conventional ligands do not effectively work[1].We happned to discover that 1,5-dilithiation of o-TMS blocked ferrocene 1 pr...展开更多
A new chiral ligand N p toluenesulfonyl 2,2′ dimethoxy 6,6′ diaminobiphenyl (Ts DMBDPPA) was prepared from 2,2′ dimethoxy 6,6′ diaminobiphenyl via N tosylation. Its Ru(II) complex was effec...A new chiral ligand N p toluenesulfonyl 2,2′ dimethoxy 6,6′ diaminobiphenyl (Ts DMBDPPA) was prepared from 2,2′ dimethoxy 6,6′ diaminobiphenyl via N tosylation. Its Ru(II) complex was effective catalysts for catalytic asymmetric transfer hydrogenation of aromatic ketones (with ee 's up to 69.3%).展开更多
A family of tropos ligands bearing a N-heterocyclic carbene and a chiral oxazoline coordination group with a N-phenyl framework were easily prepared,and their coordination behavior with Pd（Ⅱ）acetate was performed,a...A family of tropos ligands bearing a N-heterocyclic carbene and a chiral oxazoline coordination group with a N-phenyl framework were easily prepared,and their coordination behavior with Pd（Ⅱ）acetate was performed,affording a series of axially chiral palladium complexes in good yields.展开更多
This paper generally introduces the basic properties and applications of l, 1 - bi - 2 - naphthol. Especially the latest research and development on synthesis and resolution process of 1, 1 - bi - 2naphthol at home an...This paper generally introduces the basic properties and applications of l, 1 - bi - 2 - naphthol. Especially the latest research and development on synthesis and resolution process of 1, 1 - bi - 2naphthol at home and abroad was remarked.展开更多
基金the financial support by the National Natural Science Foundation of China(No.20373014).
文摘The full-parameter geometry optimization of cationic （ S ） - BINAP - Ru （ Ⅱ ） halide complex was performed by DFT method using B3LYP, PW91 and PBE potentials with several basis sets. PW91 with 3-21G / SDD basis sets is found to be the most suitable method with consideration of both precision and efficiency. The dihedral angles （ θ ） of the binaphthyl or biphenyl with different phosphorus ligand - Ru （ Ⅱ ） halide complexes were found changing from 59.9 to 79.3 degree, while the natural bite angle （ βn ） of those complexes only changes from 87.4 to 90.3 degree. It is different from the common view of asymmetric organic chemists＇ that θ directly influences βn.
基金Financial support was provided by NSFC(21922107 and 21772171)Zhejiang Provincial Natural Science Foundation of China(LR19B020001)Center of Chemistry for Frontier Technologies,and the Fundamental Research Funds for the Central Universities(2019ONA3008).
文摘As a structural analog of oxazoline,imidazoline(4,5-dihydroimidazole)has received much attention in the rational design of chiral ligands.The additional N-substituent provides broader space for fine-tuning of electronic and steric effects,and it offers a good handle for immobilizing onto solid supports.In the past decades,imidazoline ring has emerged as a powerful candidate for the design of chiral nitrogen-containing ligands,as well as a significant alternative for oxazoline ring.Various chiral imidazoline ligands have been designed and utilized in asymmetric organic reactions.These new catalysts can not only be applied in classical reactions,but also be employed to develop new organic reactions with high enantioselectivities.This review provides an overview of chiral imidazoline ligands.Their applications in asymmetric synthesis are also summarized.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 20625206 & 20372064)the National Basic Research Project (Grant Nos. 2007CB808000 & 2008CB617501), and the Chinese Academy of Sciences
文摘A series of novel N,O-type chiral ligands derived from enantiopure inherently chiral calix[4]arenes containing quinolin-2-yl-methanol moiety in the cone or partialcone conformation have been synthe-sized and characterized. Moreover,they have been applied to the catalytic asymmetric addition of diethylzinc to benzaldehyde,which represents the first example that the inherently chiral calixarene can be used as the chiral ligands for the catalytic asymmetric synthesis.
基金theMajorStateBasicResearchDevelopmentProgram (No .G2 0 0 0 0 480 0 7)andtheNationalNaturalScienceFoundationofChina (No .2 0 0 2 5 2 0 6 )
文摘Chiral ligand (R)-N, N'-Bis(2-hydroxy-3,5-di- tert-butyl-aryl-methyl)-1, 1'-binaphthalene-2,2'-diamine derived from the reduction of Schiff base (R)-2,2'-bis (3,5-di-tert-butyl-2-hy-droxybenzylideneamino)-1, 1'-binaphthyl with LiAIH(4) is fairly effective in the asymmetric addition reaction of diethylzinc to aldehydes by which good yields (46%-94%) of the corresponding sec-alcohols can be obtained in moderate ee (51%-79%) with R configuration for a variety of aldehydes.
文摘1 Results The unique structure of chiral ferrocenes allows one to design a variety of chiral phosphine ligands,which are useful tools for metal catalyzed asymmetric reactions.Although some useful chiral ferrocenyl phosphine ligands have already been reported,it is still an challenging subject tocreate new ferrocenyl phosphine ligands in order to cover asymmetric reactions in which conventional ligands do not effectively work[1].We happned to discover that 1,5-dilithiation of o-TMS blocked ferrocene 1 pr...
文摘A new chiral ligand N p toluenesulfonyl 2,2′ dimethoxy 6,6′ diaminobiphenyl (Ts DMBDPPA) was prepared from 2,2′ dimethoxy 6,6′ diaminobiphenyl via N tosylation. Its Ru(II) complex was effective catalysts for catalytic asymmetric transfer hydrogenation of aromatic ketones (with ee 's up to 69.3%).
基金the National Natural Science Foundation of China for financial support (Nos. 21372075 and 61376003)
文摘A family of tropos ligands bearing a N-heterocyclic carbene and a chiral oxazoline coordination group with a N-phenyl framework were easily prepared,and their coordination behavior with Pd（Ⅱ）acetate was performed,affording a series of axially chiral palladium complexes in good yields.
文摘This paper generally introduces the basic properties and applications of l, 1 - bi - 2 - naphthol. Especially the latest research and development on synthesis and resolution process of 1, 1 - bi - 2naphthol at home and abroad was remarked.
