The asymmetric addition of aromatic organometallic compounds to the carbonyl group(C-3)of isatins,catalyzed by transition metals,has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindo...The asymmetric addition of aromatic organometallic compounds to the carbonyl group(C-3)of isatins,catalyzed by transition metals,has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles.Here,an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides(both aryl and heteroaryl).Utilizing chiral cobalt complexes as catalysts,and the presence of a diboron reagent B_(2)nep_(2)as both a reducing agent and determinant in enantiocontrol,has resulted in the triumphantly achieved synthesis of enantioenriched products.Compared to reported strategies,this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups,such as halides and borate esters,while also eliminating the need for organometallic reagents as required in previous strategies.Through experimental investigations,the presence of aryl-cobalt species during the addition process was confirmed,rather than in-situ generation of an arylboron reagent.Furthermore,the successful attainment of the R absolute configuration through aryl addition was demonstrated.展开更多
A novel organocatalytic asymmetric approach to oxazoline derivatives that proceeds through Mannich/annulation reaction of N-acylimines with 3-chlorooxindoles is presented.This strategy provides an efficient and conven...A novel organocatalytic asymmetric approach to oxazoline derivatives that proceeds through Mannich/annulation reaction of N-acylimines with 3-chlorooxindoles is presented.This strategy provides an efficient and convenient method to access enantioenriched oxazolines such as valuable chiral S,Noxazoline ligand as well as Ferrox ligand in high yields with excellent enantio–and diastereroselectivity.Furthermore,the optically active oxazoline products can be converted to valuable 1,2-amino alcohols.More importantly,the synthetic utility of this transformation is demonstrated in the expeditious assembly of chiral Phox-type ligand,which shows excellent catalytic activities.展开更多
Axially chiral binaphthol have achieved great success in asymmetric catalysis.Compared toα-binaphthol,axially chiral aryl-β-naphthol are far less reported.Here,we report a method of asymmetric catalysis to construct...Axially chiral binaphthol have achieved great success in asymmetric catalysis.Compared toα-binaphthol,axially chiral aryl-β-naphthol are far less reported.Here,we report a method of asymmetric catalysis to constructβ-naphthol with up to 99%yield,95.5:4.5 enantiomeric ratio,using alkynyl esters as precursors and chiral phosphonic acid(CPA)/Lewis acid as catalysts.Key steps involve oxygen transfer and de novo arene formation to set up the chiral axis.Moreover,this methodology provides a versatile platform for structurally divergent synthesis of atroposelectiveβ-naphthol analogs,which are widely found in bioactive molecules and asymmetric catalysts.展开更多
Covalent organic cages(COCs)are three-dimensional organic molecules with permanent cavities,known for their ordered pore structures,excellent processability,and modular design.They have shown significant potential in ...Covalent organic cages(COCs)are three-dimensional organic molecules with permanent cavities,known for their ordered pore structures,excellent processability,and modular design.They have shown significant potential in applications such as gas adsorption,molecular separation,and catalysis.Introducing chiral elements into COCs results in chiral COCs with confined chiral cavities,which endows them with unique chiral functions and expands their application prospects.This review summarizes the research progress on chiral covalent organic cages,focusing on strategies for incorporating chiral elements,the structures and synthesis methods of representative chiral COCs,and advancements in their chiral functions.Additionally,we provide perspectives on future research directions.We hope this review will inspire further interest and creativity among researchers in the field of chiral molecular cages,leading to the development of materials with unique structures and functions.展开更多
Rational tuning of chiral nanostructures of supramolecular assemblies as catalysts and investigating their chiral morphology-enantioselectivity dependence is rarely reported. Herein, we report a series of supramolecul...Rational tuning of chiral nanostructures of supramolecular assemblies as catalysts and investigating their chiral morphology-enantioselectivity dependence is rarely reported. Herein, we report a series of supramolecular M/P-helical nanoribbons(HNs) assembled from the chiral L/D-glutamate-based amphiphiles(L/D-Glu C16) and Cu(Ⅱ) ions, with their helical screw pitches adjusted from 217 nm to 104 nm through the facile regulation of their water/organic solvent assembly environment. They were then used as ideal models to reveal the chiral morphology-enantioselectivity relationship by catalyzing the asymmetric Diels-Alder reaction. Better enantioselectivity was achieved with more twist morphology. Experimental evidences of stronger chiral transfer effect from the supramolecular HNs with more twist to the aza-chalcone as reactant were obtained to understand such dependence. Our study demonstrates a new perspective for designing supramolecular catalysts with higher enantioselectivity.展开更多
A cobalt pincer complex bearing both P and C-stereogenic centers has been designed and synthesized,allowing for the development of the first cobalt-catalyzed asymmetric hydrogenation of quinoxalines under relatively m...A cobalt pincer complex bearing both P and C-stereogenic centers has been designed and synthesized,allowing for the development of the first cobalt-catalyzed asymmetric hydrogenation of quinoxalines under relatively mild conditions.Valuable chiral 1,2,3,4-tetrahydroquinoxalines could be obtained with high yields and excellent enantioselectivities(35 examples,up to>99%ee).展开更多
A wide range of isoquinoline ring-modified Quinap oxides with different steric and electronic variations have been constructed through a palladium-catalyzed imidoylative cyclization of arylethenyl isocyanides with 2-d...A wide range of isoquinoline ring-modified Quinap oxides with different steric and electronic variations have been constructed through a palladium-catalyzed imidoylative cyclization of arylethenyl isocyanides with 2-diphenylphosphinyl-1-naphthyl bromides.The Pd-catalysis plays dual roles in the formation of both axial C–C bond and isoquinoline ring.This de novo synthetic strategy features good functional group tolerance,high yields and easy scale-up,providing Quinap derivatives with substitution patterns that could not be obtained using coupling reactions.Chiral ligands 7 and 12 can be readily prepared by transformation of the resulting Quinap oxide to their BINOL esters,and have been proven to be superb chiral ligands for the copper-catalyzed enantioselective A^(3)-coupling and alkynylation of quinoline reactions.In general,the enantioselectivies obtained using ligands 7 and 12 are excellent,and the ee values are higher than those using Quinap as ligand,even three times higher in some cases.Mechanism studies revealed that a monomeric copper(Ⅰ)complex bearing a single chiral ligand was formed and served as the catalytically active species.展开更多
The catalytic asymmetric dipolar cycloaddition reaction is efficient for the construction of various chiral valuable carbo-and heterocycles.Thus,the design and exploration of new dipoles and the subsequent control of ...The catalytic asymmetric dipolar cycloaddition reaction is efficient for the construction of various chiral valuable carbo-and heterocycles.Thus,the design and exploration of new dipoles and the subsequent control of their reactivity for various stereoselective cycloadditions are significant aspects of modern organic synthesis.Herein,we have developed a series of vinyl cyclic carbamates containing an oxazolidine-2,4–dione fragment and used them as reactive precursors for in situ generation of amide-based aza-π-allylpalladium 1,3-dipoles,which could be applied to asymmetric decarboxylative 1,3-dipolar cycloaddition with different types of dipolarophiles containing C=C,C=N,and C=O double bonds.This strategy provides an opportunity for the synthesis of previously unusual structures,such as highly functionalized optically pure pyrrolidin-2-ones,imidazolidin-4-ones,and oxazolidin-4-ones.This protocol also has significant features including wide substrate scope,mild reaction conditions,simple operation,and good to excellent results(70 examples,up to 99%yield,>20:1 dr and 99%ee).This unique method significantly expands the reaction range of the amide-based aza-π-allylpalladium 1,3-dipoles compared to the precedents.展开更多
A novel and readily available binaphthyl-based fluorescent probe(S)-1 was designed and synthesized.(S)-1 can be used to not only chemoselectively discriminate 3 basic amino acids out of common amino acids,but also ena...A novel and readily available binaphthyl-based fluorescent probe(S)-1 was designed and synthesized.(S)-1 can be used to not only chemoselectively discriminate 3 basic amino acids out of common amino acids,but also enantioselectively recognize histidine.Encouragingly,enantioselective imaging of histidine in cells was achieved for the first time by the probe(S)-1.These performances endowed it potential application in the chiral analysis of basic amino acids in asymmetric synthesis and cell imaging for diagnosis of diseases caused by racemization of histidine.Nuclear magnetic resonance(NMR)and mass spectrometry investigations suggested that different reaction extent of(S)-1 with L/D-histidine and different product structures generated the observed enantioselective fluorescent response.The molecular structures and thermodynamic stability of the complexes,formed from(S)-1+Zn2+and enantiomers of histidine,were calculated by Gaussian 16 based on density functional theory(DFT)to validate the above action mechanism.展开更多
Metal-catalyzed alkene arylalkoxylation is a powerful complexity-building strategy for the synthesis of oxygen heterocycles from simpleγ-unsaturated alcohols,but only a few examples of catalytic enantioselective meth...Metal-catalyzed alkene arylalkoxylation is a powerful complexity-building strategy for the synthesis of oxygen heterocycles from simpleγ-unsaturated alcohols,but only a few examples of catalytic enantioselective methods exist.Herein,an efficient palladium-catalyzed enantioselective arylalkoxylation ofγ-hydroxyalkenes with aryl halides is reported.The salient features of this transformation include a remarkable broad substrate scope,mild reaction conditions,and good functional group tolerance,delivering a series of chiral tetrahydrofurans containing a tertiary or quaternary stereocenter in good yields with up to 95%ee.The Xu10 ligand with a suitable side-arm was responsible for the high reactivity and good enantioselectivity of this transformation.展开更多
Herein,a layered chiral coordination polymer,[Cd2(D‑cam)_(2)(2,2′‑bipy)_(2)]_(n)(Cd‑CP),was synthesized using a solvothermal method with camphoric acid(D‑H_(2)cam),2,2′‑bipyridine(2,2′‑bipy)and Cd^(2+),and Tb^(3+)@...Herein,a layered chiral coordination polymer,[Cd2(D‑cam)_(2)(2,2′‑bipy)_(2)]_(n)(Cd‑CP),was synthesized using a solvothermal method with camphoric acid(D‑H_(2)cam),2,2′‑bipyridine(2,2′‑bipy)and Cd^(2+),and Tb^(3+)@Cd‑CP was in‑situ synthesized introducing Tb^(3+)ions.The fluorescence experiments revealed that compared to Cd‑CP,Tb^(3+)@Cd‑CP exhibited ultra‑high fluorescence performance.The luminescence sensing performance demonstrated that Tb^(3+)@Cd‑CP could distinguish R/S‑propylene glycol(R/S‑PG)by fluorescence responses,with fluorescence quenching constant of 5.3×10^(3)and 2.0×10^(3)L·mol^(-1)respectively and the enantioselectivity factor(α)of 2.65.Moreover,Tb^(3+)@Cd‑CP demonstrated limits of detection of 9.3 and 19.0μmol·L^(-1)for R‑PG and S‑PG,respectively,and showed good reproducibility.展开更多
The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable,but remain a big challenge.Herein,we reported the first rhodium(Ⅲ)-catalyzed as...The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable,but remain a big challenge.Herein,we reported the first rhodium(Ⅲ)-catalyzed asymmetric intramolecular C-H macrocyclization,enabling the efficient synthesis of structurally diverse enantioenriched macrocycles.This robust enantioselective C-H macrocyclization has a broad functional group tolerance,excellent enantioselectivities(up to 98.5:1.5 e.r.)and a mild reaction condition,releasing CO_(2)as the single by-product.More significantly,the resulting unique enantioenriched19-membered macrocycle 2f was found to demonstrate a potent in vitro anti-Zika virus(ZIKV)activity without obvious cytotoxicity.Further investigation revealed that the anti-ZIKV activity is presumably attributed to an autophagy inhibition in the early stage of viral infection by down-regulating the expression of autophagy related gene Atg12.展开更多
Zeolites are crystalline porous materials that are used in the chemical industry for adsorption, separation and catalytic reactions. Chiral zeolites have shown promise in enantioselective adsorption and catalytic orga...Zeolites are crystalline porous materials that are used in the chemical industry for adsorption, separation and catalytic reactions. Chiral zeolites have shown promise in enantioselective adsorption and catalytic organic reactions, attracting significant research interest. Recent advances have been made in the rational design, computational prediction and hydrothermal synthesis of using chiral organic structure-directing agents. Additionally, newly developed electron microscopic techniques have been utilized to analyze the structure and determine absolute configuration. The following review aims to provide an overview of the development history of chiral zeolites, examine several prominent chiral zeolite structures discovered so far, discuss the recent progress in characterization methods and explore their potential applications.展开更多
A rhodium-catalyzed desymmetrization reaction for enantioselective methyl C-H arylation is achieved by utilizing an in situ arylating reagent via nucleophilic cyclization of o-aminoaryl alkyne.The reaction results in ...A rhodium-catalyzed desymmetrization reaction for enantioselective methyl C-H arylation is achieved by utilizing an in situ arylating reagent via nucleophilic cyclization of o-aminoaryl alkyne.The reaction results in chiral indoles containing all-carbon quaternary stereocenters under atmospheric conditions,with a wide range of substrates exhibiting good enantioselectivity(44 examples).Mechnism and DFT studies show that the stereocontrol is reasonably achieved through the collaborative control of a large silicon substituted chiral ligand and C-H···π,LP···πinteractions between aryl rings of the carboxylate group and the substrate.Control experiments demonstrate that Rh-aryl bond formation via in situ nucleophilic cyclization is more critical for reaction efficiency than via C-H activation of the nucleophilic cyclization byproduct.展开更多
A rhodium(Ⅲ)-catalyzed hydrosilylation/cyclization reaction of cyclohexadienone-tetheredα,β-unsaturated aldehydes(1,6-dienes)with triethylsilane is described,providing a series of cishydrobenzofurans,cis-hydroindol...A rhodium(Ⅲ)-catalyzed hydrosilylation/cyclization reaction of cyclohexadienone-tetheredα,β-unsaturated aldehydes(1,6-dienes)with triethylsilane is described,providing a series of cishydrobenzofurans,cis-hydroindoles,and cishydroindenes bearing silyl enol ether in good to excellent yields and excellent stereoselectivities.Additionally,the versatility of this method was demonstrated through a gram-scale experiment and various downstream transformations,highlighting its utility.展开更多
The Ni(Ⅱ)-chiral(4S,4'S)-2,2'-(4,6-dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole](DBFOX/Ph)-catalyzed asymmetric 1,3-dipolar cycloadditions of nitrile imines to N-α,β-unsaturated acylpyrazoles was presen...The Ni(Ⅱ)-chiral(4S,4'S)-2,2'-(4,6-dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole](DBFOX/Ph)-catalyzed asymmetric 1,3-dipolar cycloadditions of nitrile imines to N-α,β-unsaturated acylpyrazoles was presented.This tactic rendered a facile and feasible route to prepare the optically active tetrasubstituted 5-3,5-dimethylpyrazole acyl dihydropyrazole cy-cloadducts bearing one or two contiguous stereocenters in good yields(up to 97%yield)with high regioselectivities(100%)and enantioselectivities(up to 97.5%ee).Following that,chiral cycloadducts could be obtained consistently in good chemical yields with excellent enantioselectivities within the gram scale process,additionally,toward five kinds of derivatization reac-tions like nucleophilic and reduction for further conversion of chiral cycloadducts to related chiral dihydropyrazole derivatives encompassing different substituents.展开更多
An operationally simple protocol was designed for the enantioselective silane reduction (ESR) of ketones using air- and moisture-stable [Ir(OMe)(cod)]<sub>2</sub> (cod = 1,5-cyclooctadiene) (3) as a metal ...An operationally simple protocol was designed for the enantioselective silane reduction (ESR) of ketones using air- and moisture-stable [Ir(OMe)(cod)]<sub>2</sub> (cod = 1,5-cyclooctadiene) (3) as a metal catalyst precursor. This reaction was driven by chiral hydroxyamide-functionalized azolium salt 2. The catalytic ESR reaction could be performed under benchtop conditions at room temperature. Treatment of 2 with 3 in THF yielded the monodentate IrCl(NHC)(cod) (NHC = N-heterocyclic carbene) complex 4 in 93% yield, herein the anionic methoxy ligand of 3 serves as an internal base that deprotonates the azolium ring of 2. The well-defined Ir complex 4 catalyzed the ESR reaction of propiophenone (6) with (EtO)<sub>2</sub>MeSiH using the pre-mixing reaction procedure. Based on this success, the catalytic ESR reaction was designed and implemented using an in situ-generated NHC/Ir catalyst derived from 2 and 3. Thus, a wide variety of aryl ketones could be reduced to the corresponding optically active alcohols in moderate to excellent stereoselectivities at room temperature without temperature control. Since the high catalytic activity of 3 was observed, we next evaluated several other transition metal catalyst precursors for the catalytic ESR reaction under the influence of 2. This evaluation revealed that Ir(acac)(cod) (acac = acetylacetonate) (28) and [IrCl(cod)]<sub>2</sub> (5) can be successfully used as metal catalyst precursors in the ESR reaction.展开更多
Regioselective and enantioselective hydroxylation of propargylic C-H bonds are useful reactions but often lack appropriate catalysts.Here a green and efficient asymmetric hydroxylation of primary and secondary C-H bon...Regioselective and enantioselective hydroxylation of propargylic C-H bonds are useful reactions but often lack appropriate catalysts.Here a green and efficient asymmetric hydroxylation of primary and secondary C-H bonds at propargylic positions has been established.A series of optically active propargylic alcohols were prepared with high regio-and enantioselectivity(up to 99%ee)under mild reaction conditions by using P450tol,while the C≡C bonds in the molecule remained unreacted.This protocol provides a green and practical method for constructing enantiomerically chiral propargylic alcohols.In addition,we also demonstrated that the biohydroxylation strategy was able to scaled up to 2.25 mmol scale with the production of chiral propargyl alcohol 2a at a yield of 196 mg with 96%ee,which’s an important synthetic intermediate of antifungal drug Ravuconazole.展开更多
Nineβ‐cyclodextrin derivatives containing an amino group were synthesized via nucleophilic sub‐stitution from mono（6‐O‐p‐tolylsulfonyl）‐β‐cyclodextrin and used in asymmetric biomimetic Mi‐chael addition re...Nineβ‐cyclodextrin derivatives containing an amino group were synthesized via nucleophilic sub‐stitution from mono（6‐O‐p‐tolylsulfonyl）‐β‐cyclodextrin and used in asymmetric biomimetic Mi‐chael addition reactions in water at room temperature. The mechanism responsible for the moder‐ate activity and enantioselectivity of the β‐cyclodextrin derivatives was explored using nuclear magnetic resonance spectroscopy, namely 2D 1H rotating‐frame overhauser effect spectroscopy （ROESY）, ultraviolet absorption spectroscopy, and quantum chemical calculations, which provide a useful technique for investigating the formation of inclusion complexes. The effects of the pH of the reaction medium, theβ‐cyclodextrin derivative dosage, the structure of the modifying amino group, and various substrates on the yield and enantioselectivity were investigated. The results indicated that these factors had an important effect on the enantiomeric excess （ee） in the reaction system. Experiments using a competitor for inclusion complex formation showed that a hydrophobic cavity is necessary for enantioselective Michael addition. A comparison of the reactions using 4‐nitro‐β‐nitrostyrene and 2‐nitro‐β‐nitrostyrene showed that steric hindrance improved the enan‐tioselectivity. This was verified by the optimized geometries obtained from quantum chemical cal‐culations. An ee of 71%was obtained in the asymmetric Michael addition of cyclohexanone and 2‐nitro‐β‐nitrostyrene, using （S）‐2‐aminomethylpyrrolidine‐modified β‐CD as the catalyst, in an aqueous buffer solution, i.e., CH3COONa‐HCl （pH 7.5）.展开更多
The chiral nature of biological systems enables their stereoselective interaction with chiral compounds. It has been well documented that the enantiomers ofa chiral drug may show differences in drug disposition especi...The chiral nature of biological systems enables their stereoselective interaction with chiral compounds. It has been well documented that the enantiomers ofa chiral drug may show differences in drug disposition especially in metabolic behavior. As a result, it is of vital importance to separate the enantiomers of a chiral drug in metabolic studies. This paper discusses enantioselective methods （include high-performance liquid chromatography, gas chromatography, capillary electrophoresis and high-performance liquid chromatography-mass spectrometry） that applied in chiral drug metabolism, using most recent examples where possible.展开更多
基金the National Key R&D Program of China(No.2022YFA1503200)the National Natural Science Foundation of China(Nos.22025104,22171134,and 21972064)the Fundamental Research Funds for the Central Universities(No.020514380254)is greatly appreciated.
文摘The asymmetric addition of aromatic organometallic compounds to the carbonyl group(C-3)of isatins,catalyzed by transition metals,has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles.Here,an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides(both aryl and heteroaryl).Utilizing chiral cobalt complexes as catalysts,and the presence of a diboron reagent B_(2)nep_(2)as both a reducing agent and determinant in enantiocontrol,has resulted in the triumphantly achieved synthesis of enantioenriched products.Compared to reported strategies,this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups,such as halides and borate esters,while also eliminating the need for organometallic reagents as required in previous strategies.Through experimental investigations,the presence of aryl-cobalt species during the addition process was confirmed,rather than in-situ generation of an arylboron reagent.Furthermore,the successful attainment of the R absolute configuration through aryl addition was demonstrated.
基金Qingdao Marine Science and Technology Center(No.2022QNLM030003–2)the Fundamental Research Funds for the Central Universities,Taishan Scholar Program of Shandong Province(No.tsqn202103152)+2 种基金National Natural Science Foundation of China(No.22201270)Natural Science Foundation of Shandong Province(No.ZR2021QB033)the National Key Research and Development Program of China(No.2022YFC2804400)for financial support。
文摘A novel organocatalytic asymmetric approach to oxazoline derivatives that proceeds through Mannich/annulation reaction of N-acylimines with 3-chlorooxindoles is presented.This strategy provides an efficient and convenient method to access enantioenriched oxazolines such as valuable chiral S,Noxazoline ligand as well as Ferrox ligand in high yields with excellent enantio–and diastereroselectivity.Furthermore,the optically active oxazoline products can be converted to valuable 1,2-amino alcohols.More importantly,the synthetic utility of this transformation is demonstrated in the expeditious assembly of chiral Phox-type ligand,which shows excellent catalytic activities.
基金financial support from the National Natural Science Foundation of China(Nos.22071062,22001077 and 22271096)Guangdong Science and Technology Department(Nos.2021A1515012331,2023A1515011001)+1 种基金the Fundamental Research Funds for the Central Universities(No.2022ZYGXZR016)South China University of Technology for start-up funds。
文摘Axially chiral binaphthol have achieved great success in asymmetric catalysis.Compared toα-binaphthol,axially chiral aryl-β-naphthol are far less reported.Here,we report a method of asymmetric catalysis to constructβ-naphthol with up to 99%yield,95.5:4.5 enantiomeric ratio,using alkynyl esters as precursors and chiral phosphonic acid(CPA)/Lewis acid as catalysts.Key steps involve oxygen transfer and de novo arene formation to set up the chiral axis.Moreover,this methodology provides a versatile platform for structurally divergent synthesis of atroposelectiveβ-naphthol analogs,which are widely found in bioactive molecules and asymmetric catalysts.
基金supported by the National Natural Science Foundation of China(Grant Nos.22271164 and U20A20259 and 22371147)the Fundamental Research Funds for the Central Universities,the NCC Fund(Grant No.NCC2020FH04)+1 种基金the Tianshan Innovation Team Plan of Xinjiang Uygur Autonomous Region(Grant No.2023D14002)Nankai University(NKU).
文摘Covalent organic cages(COCs)are three-dimensional organic molecules with permanent cavities,known for their ordered pore structures,excellent processability,and modular design.They have shown significant potential in applications such as gas adsorption,molecular separation,and catalysis.Introducing chiral elements into COCs results in chiral COCs with confined chiral cavities,which endows them with unique chiral functions and expands their application prospects.This review summarizes the research progress on chiral covalent organic cages,focusing on strategies for incorporating chiral elements,the structures and synthesis methods of representative chiral COCs,and advancements in their chiral functions.Additionally,we provide perspectives on future research directions.We hope this review will inspire further interest and creativity among researchers in the field of chiral molecular cages,leading to the development of materials with unique structures and functions.
基金support of this research by the National Natural Science Foundation of China(Nos.22202171,21922202,and 22272146)the Natural Science Foundation of Jiangsu Basic Research Program(No.BK20220559)+1 种基金the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(No.22KJD150009)the Jiangsu Specially-Appointed Professor Plan(Z.Xi)from the Jiangsu Education Department。
文摘Rational tuning of chiral nanostructures of supramolecular assemblies as catalysts and investigating their chiral morphology-enantioselectivity dependence is rarely reported. Herein, we report a series of supramolecular M/P-helical nanoribbons(HNs) assembled from the chiral L/D-glutamate-based amphiphiles(L/D-Glu C16) and Cu(Ⅱ) ions, with their helical screw pitches adjusted from 217 nm to 104 nm through the facile regulation of their water/organic solvent assembly environment. They were then used as ideal models to reveal the chiral morphology-enantioselectivity relationship by catalyzing the asymmetric Diels-Alder reaction. Better enantioselectivity was achieved with more twist morphology. Experimental evidences of stronger chiral transfer effect from the supramolecular HNs with more twist to the aza-chalcone as reactant were obtained to understand such dependence. Our study demonstrates a new perspective for designing supramolecular catalysts with higher enantioselectivity.
基金the financial support of the National Natural Science Foundation of China(No.21672133)the Opening Foundation of Key Laboratory of Applied Surface and Colloid Chemistry,Ministry of Education(No.GK202205011)the Fundamental Research Funds for the Central Universities(Nos.GK202307007 and GK202002003)。
文摘A cobalt pincer complex bearing both P and C-stereogenic centers has been designed and synthesized,allowing for the development of the first cobalt-catalyzed asymmetric hydrogenation of quinoxalines under relatively mild conditions.Valuable chiral 1,2,3,4-tetrahydroquinoxalines could be obtained with high yields and excellent enantioselectivities(35 examples,up to>99%ee).
基金Financial support from the National Natural Science Foundation of China(No.22171168)Excellent Youth Foundation of Henan Scientific Committee(No.222300420012)Taishan Scholar Program of Shandong Province is gratefully acknowledged。
文摘A wide range of isoquinoline ring-modified Quinap oxides with different steric and electronic variations have been constructed through a palladium-catalyzed imidoylative cyclization of arylethenyl isocyanides with 2-diphenylphosphinyl-1-naphthyl bromides.The Pd-catalysis plays dual roles in the formation of both axial C–C bond and isoquinoline ring.This de novo synthetic strategy features good functional group tolerance,high yields and easy scale-up,providing Quinap derivatives with substitution patterns that could not be obtained using coupling reactions.Chiral ligands 7 and 12 can be readily prepared by transformation of the resulting Quinap oxide to their BINOL esters,and have been proven to be superb chiral ligands for the copper-catalyzed enantioselective A^(3)-coupling and alkynylation of quinoline reactions.In general,the enantioselectivies obtained using ligands 7 and 12 are excellent,and the ee values are higher than those using Quinap as ligand,even three times higher in some cases.Mechanism studies revealed that a monomeric copper(Ⅰ)complex bearing a single chiral ligand was formed and served as the catalytically active species.
基金the National Natural Science Foundation of China(Nos.22271027,22171029,21901024,21871252,21801024,and 21801026)the Sichuan Science and Technology Program(No.2021YFS0315)the Talent Program of Chengdu University(Nos.2081919035 and 2081921038)。
文摘The catalytic asymmetric dipolar cycloaddition reaction is efficient for the construction of various chiral valuable carbo-and heterocycles.Thus,the design and exploration of new dipoles and the subsequent control of their reactivity for various stereoselective cycloadditions are significant aspects of modern organic synthesis.Herein,we have developed a series of vinyl cyclic carbamates containing an oxazolidine-2,4–dione fragment and used them as reactive precursors for in situ generation of amide-based aza-π-allylpalladium 1,3-dipoles,which could be applied to asymmetric decarboxylative 1,3-dipolar cycloaddition with different types of dipolarophiles containing C=C,C=N,and C=O double bonds.This strategy provides an opportunity for the synthesis of previously unusual structures,such as highly functionalized optically pure pyrrolidin-2-ones,imidazolidin-4-ones,and oxazolidin-4-ones.This protocol also has significant features including wide substrate scope,mild reaction conditions,simple operation,and good to excellent results(70 examples,up to 99%yield,>20:1 dr and 99%ee).This unique method significantly expands the reaction range of the amide-based aza-π-allylpalladium 1,3-dipoles compared to the precedents.
基金financial support from the National Natural Science Foundation of China(Nos.22074114,22377097,21877087)Natural Science Foundation of Hubei Province of China(Nos.2020CFB623,2021CFB556)+2 种基金Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education(No.LCX202305)Wuhan Institute of Technology Graduate Education and Teaching Reform Research Project(Nos.2022JYXM09,2021JYXM07)Wuhan Institute of Technology Graduate Innovation Fund(No.CX2022450)are greatly appreciated。
文摘A novel and readily available binaphthyl-based fluorescent probe(S)-1 was designed and synthesized.(S)-1 can be used to not only chemoselectively discriminate 3 basic amino acids out of common amino acids,but also enantioselectively recognize histidine.Encouragingly,enantioselective imaging of histidine in cells was achieved for the first time by the probe(S)-1.These performances endowed it potential application in the chiral analysis of basic amino acids in asymmetric synthesis and cell imaging for diagnosis of diseases caused by racemization of histidine.Nuclear magnetic resonance(NMR)and mass spectrometry investigations suggested that different reaction extent of(S)-1 with L/D-histidine and different product structures generated the observed enantioselective fluorescent response.The molecular structures and thermodynamic stability of the complexes,formed from(S)-1+Zn2+and enantiomers of histidine,were calculated by Gaussian 16 based on density functional theory(DFT)to validate the above action mechanism.
基金funding support of the National Natural Science Foundation of China(NSFC,Nos.22071060 and 22031004)the National Key R&D Program of China(No.2021YFF0701600)Shanghai Municipal Education Commission(No.20212308)。
文摘Metal-catalyzed alkene arylalkoxylation is a powerful complexity-building strategy for the synthesis of oxygen heterocycles from simpleγ-unsaturated alcohols,but only a few examples of catalytic enantioselective methods exist.Herein,an efficient palladium-catalyzed enantioselective arylalkoxylation ofγ-hydroxyalkenes with aryl halides is reported.The salient features of this transformation include a remarkable broad substrate scope,mild reaction conditions,and good functional group tolerance,delivering a series of chiral tetrahydrofurans containing a tertiary or quaternary stereocenter in good yields with up to 95%ee.The Xu10 ligand with a suitable side-arm was responsible for the high reactivity and good enantioselectivity of this transformation.
文摘Herein,a layered chiral coordination polymer,[Cd2(D‑cam)_(2)(2,2′‑bipy)_(2)]_(n)(Cd‑CP),was synthesized using a solvothermal method with camphoric acid(D‑H_(2)cam),2,2′‑bipyridine(2,2′‑bipy)and Cd^(2+),and Tb^(3+)@Cd‑CP was in‑situ synthesized introducing Tb^(3+)ions.The fluorescence experiments revealed that compared to Cd‑CP,Tb^(3+)@Cd‑CP exhibited ultra‑high fluorescence performance.The luminescence sensing performance demonstrated that Tb^(3+)@Cd‑CP could distinguish R/S‑propylene glycol(R/S‑PG)by fluorescence responses,with fluorescence quenching constant of 5.3×10^(3)and 2.0×10^(3)L·mol^(-1)respectively and the enantioselectivity factor(α)of 2.65.Moreover,Tb^(3+)@Cd‑CP demonstrated limits of detection of 9.3 and 19.0μmol·L^(-1)for R‑PG and S‑PG,respectively,and showed good reproducibility.
基金supported by National Natural Science Foundation of China(No.81973166)Science and Technology Commission of Shanghai Municipality(No.22XD1424600)+4 种基金Natural Science Foundation of Shanghai Municipality(No.22ZR1474100)Taishan Scholar Foundation of Shandong Province(No.tsqn202306322)National Key R&D Program of China(No.2021YFC2300700)Shandong Laboratory Program(No.SYS202205)Shandong Provincial Natural Science Foundation(Nos.ZR2023LSW003 and ZR2023JQ028)。
文摘The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable,but remain a big challenge.Herein,we reported the first rhodium(Ⅲ)-catalyzed asymmetric intramolecular C-H macrocyclization,enabling the efficient synthesis of structurally diverse enantioenriched macrocycles.This robust enantioselective C-H macrocyclization has a broad functional group tolerance,excellent enantioselectivities(up to 98.5:1.5 e.r.)and a mild reaction condition,releasing CO_(2)as the single by-product.More significantly,the resulting unique enantioenriched19-membered macrocycle 2f was found to demonstrate a potent in vitro anti-Zika virus(ZIKV)activity without obvious cytotoxicity.Further investigation revealed that the anti-ZIKV activity is presumably attributed to an autophagy inhibition in the early stage of viral infection by down-regulating the expression of autophagy related gene Atg12.
基金Financial support from Institute of Chemistry, Chinese Academy of Sciences。
文摘Zeolites are crystalline porous materials that are used in the chemical industry for adsorption, separation and catalytic reactions. Chiral zeolites have shown promise in enantioselective adsorption and catalytic organic reactions, attracting significant research interest. Recent advances have been made in the rational design, computational prediction and hydrothermal synthesis of using chiral organic structure-directing agents. Additionally, newly developed electron microscopic techniques have been utilized to analyze the structure and determine absolute configuration. The following review aims to provide an overview of the development history of chiral zeolites, examine several prominent chiral zeolite structures discovered so far, discuss the recent progress in characterization methods and explore their potential applications.
基金financial support for this work from the National Key R&D Program of China(No.2021YFC0864700)the National Natural Science Foundation of China(Nos.21801066,U1804283 and 82130103)+2 种基金the Central Plains Scholars and Scientists Studio Fund(No.2018002)the project funded by the Natural Science Foundation of Henan(Nos.222300420056,222300420204)the China Postdoctoral Science Foundation(Nos.2020M682307,2021T140183)。
文摘A rhodium-catalyzed desymmetrization reaction for enantioselective methyl C-H arylation is achieved by utilizing an in situ arylating reagent via nucleophilic cyclization of o-aminoaryl alkyne.The reaction results in chiral indoles containing all-carbon quaternary stereocenters under atmospheric conditions,with a wide range of substrates exhibiting good enantioselectivity(44 examples).Mechnism and DFT studies show that the stereocontrol is reasonably achieved through the collaborative control of a large silicon substituted chiral ligand and C-H···π,LP···πinteractions between aryl rings of the carboxylate group and the substrate.Control experiments demonstrate that Rh-aryl bond formation via in situ nucleophilic cyclization is more critical for reaction efficiency than via C-H activation of the nucleophilic cyclization byproduct.
基金financial support from the National Key R&D Program of China(No.2022YFF1202600)the National Natural Science Foundation of China(Nos.22001172,22071155,and22371188)+4 种基金the Science and Technology Commission of Shanghai Municipality(Nos.20XD1403600 and 20400750300)the Shanghai Municipal Education Commission(No.2019-01-07-00-10-E00072)the Innovation Team and Talents Cultivation Program of National Administration of Traditional Chinese Medicine(No.ZYYCXTD-202004)the Shanghai Municipal Health Commission/Shanghai Municipal Administration of Traditional Chinese Medicine[No.ZY(2021-2023)-0501]Organizational Key R&D Program of SHUTCM(No.2023YZZ01)。
文摘A rhodium(Ⅲ)-catalyzed hydrosilylation/cyclization reaction of cyclohexadienone-tetheredα,β-unsaturated aldehydes(1,6-dienes)with triethylsilane is described,providing a series of cishydrobenzofurans,cis-hydroindoles,and cishydroindenes bearing silyl enol ether in good to excellent yields and excellent stereoselectivities.Additionally,the versatility of this method was demonstrated through a gram-scale experiment and various downstream transformations,highlighting its utility.
基金Project supported by the National Natural Science Foundation of China(Nos.22278098,21908034,22008045)the Natural Science Foundation of Heilongjiang Province(Nos.LH2021H001,LH2023B013)。
文摘The Ni(Ⅱ)-chiral(4S,4'S)-2,2'-(4,6-dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole](DBFOX/Ph)-catalyzed asymmetric 1,3-dipolar cycloadditions of nitrile imines to N-α,β-unsaturated acylpyrazoles was presented.This tactic rendered a facile and feasible route to prepare the optically active tetrasubstituted 5-3,5-dimethylpyrazole acyl dihydropyrazole cy-cloadducts bearing one or two contiguous stereocenters in good yields(up to 97%yield)with high regioselectivities(100%)and enantioselectivities(up to 97.5%ee).Following that,chiral cycloadducts could be obtained consistently in good chemical yields with excellent enantioselectivities within the gram scale process,additionally,toward five kinds of derivatization reac-tions like nucleophilic and reduction for further conversion of chiral cycloadducts to related chiral dihydropyrazole derivatives encompassing different substituents.
文摘An operationally simple protocol was designed for the enantioselective silane reduction (ESR) of ketones using air- and moisture-stable [Ir(OMe)(cod)]<sub>2</sub> (cod = 1,5-cyclooctadiene) (3) as a metal catalyst precursor. This reaction was driven by chiral hydroxyamide-functionalized azolium salt 2. The catalytic ESR reaction could be performed under benchtop conditions at room temperature. Treatment of 2 with 3 in THF yielded the monodentate IrCl(NHC)(cod) (NHC = N-heterocyclic carbene) complex 4 in 93% yield, herein the anionic methoxy ligand of 3 serves as an internal base that deprotonates the azolium ring of 2. The well-defined Ir complex 4 catalyzed the ESR reaction of propiophenone (6) with (EtO)<sub>2</sub>MeSiH using the pre-mixing reaction procedure. Based on this success, the catalytic ESR reaction was designed and implemented using an in situ-generated NHC/Ir catalyst derived from 2 and 3. Thus, a wide variety of aryl ketones could be reduced to the corresponding optically active alcohols in moderate to excellent stereoselectivities at room temperature without temperature control. Since the high catalytic activity of 3 was observed, we next evaluated several other transition metal catalyst precursors for the catalytic ESR reaction under the influence of 2. This evaluation revealed that Ir(acac)(cod) (acac = acetylacetonate) (28) and [IrCl(cod)]<sub>2</sub> (5) can be successfully used as metal catalyst precursors in the ESR reaction.
基金financial support from the National Natural Science Foundation of China(No.32271537 and 22061049)the Science and Technology Department of Guizhou province(QKHJCZK2021-036 and QKHRCPTGCC-2023-003)+1 种基金the Science and Technology Department of Zunyi(ZSKRPT-2020-5,ZSKH-2018-3,ZSKRPT-2021-5)Zunyi Medical University(QKH-2018-5772-014).
文摘Regioselective and enantioselective hydroxylation of propargylic C-H bonds are useful reactions but often lack appropriate catalysts.Here a green and efficient asymmetric hydroxylation of primary and secondary C-H bonds at propargylic positions has been established.A series of optically active propargylic alcohols were prepared with high regio-and enantioselectivity(up to 99%ee)under mild reaction conditions by using P450tol,while the C≡C bonds in the molecule remained unreacted.This protocol provides a green and practical method for constructing enantiomerically chiral propargylic alcohols.In addition,we also demonstrated that the biohydroxylation strategy was able to scaled up to 2.25 mmol scale with the production of chiral propargyl alcohol 2a at a yield of 196 mg with 96%ee,which’s an important synthetic intermediate of antifungal drug Ravuconazole.
基金supported by the National Natural Science Foundation of China (21425627,21376279)~~
文摘Nineβ‐cyclodextrin derivatives containing an amino group were synthesized via nucleophilic sub‐stitution from mono（6‐O‐p‐tolylsulfonyl）‐β‐cyclodextrin and used in asymmetric biomimetic Mi‐chael addition reactions in water at room temperature. The mechanism responsible for the moder‐ate activity and enantioselectivity of the β‐cyclodextrin derivatives was explored using nuclear magnetic resonance spectroscopy, namely 2D 1H rotating‐frame overhauser effect spectroscopy （ROESY）, ultraviolet absorption spectroscopy, and quantum chemical calculations, which provide a useful technique for investigating the formation of inclusion complexes. The effects of the pH of the reaction medium, theβ‐cyclodextrin derivative dosage, the structure of the modifying amino group, and various substrates on the yield and enantioselectivity were investigated. The results indicated that these factors had an important effect on the enantiomeric excess （ee） in the reaction system. Experiments using a competitor for inclusion complex formation showed that a hydrophobic cavity is necessary for enantioselective Michael addition. A comparison of the reactions using 4‐nitro‐β‐nitrostyrene and 2‐nitro‐β‐nitrostyrene showed that steric hindrance improved the enan‐tioselectivity. This was verified by the optimized geometries obtained from quantum chemical cal‐culations. An ee of 71%was obtained in the asymmetric Michael addition of cyclohexanone and 2‐nitro‐β‐nitrostyrene, using （S）‐2‐aminomethylpyrrolidine‐modified β‐CD as the catalyst, in an aqueous buffer solution, i.e., CH3COONa‐HCl （pH 7.5）.
基金National Natural Science Foundation of China(Grant No.30225047 and 30701038)
文摘The chiral nature of biological systems enables their stereoselective interaction with chiral compounds. It has been well documented that the enantiomers ofa chiral drug may show differences in drug disposition especially in metabolic behavior. As a result, it is of vital importance to separate the enantiomers of a chiral drug in metabolic studies. This paper discusses enantioselective methods （include high-performance liquid chromatography, gas chromatography, capillary electrophoresis and high-performance liquid chromatography-mass spectrometry） that applied in chiral drug metabolism, using most recent examples where possible.
