Co-assembling chiral molecules with achiral compounds via non-covalent interactions like areneperfluoroarene(AP) interactions offers an effective approach for fabricating chiral functional materials.Herein,chiral mole...Co-assembling chiral molecules with achiral compounds via non-covalent interactions like areneperfluoroarene(AP) interactions offers an effective approach for fabricating chiral functional materials.Herein,chiral molecules L/D-PF1 and L/D-PF2 with pyrene groups were synthesized and its chiroptical properties upon co-assembly with achiral compound octafluoronaphthalene(OFN) through AP interaction were systemically studied.The co-assembly of L/D-PF1/OFN and L/D-PF2/OFN exhibited distinct chiroptical properties such as circular dichroism(CD) and circularly polarized luminescence(CPL) signals.Chirality transfer from the chirality center of L/D-PF1 and L/D-PF2 to the achiral OFN and chiral amplification were successfully achieved.Besides,no significant CPL signal was observed in the self-assembly of L/DPF1 or L/D-PF2 while co-assembly with OFN exhibited obvious CPL amplification induced by AP interaction.Notably,a reversal CD signal and CPL signal could be observed in L/D-PF2/OFN when the molar ratio changed from 1:1 to 1:2 while not found in L/D-PF1/OFN,indicating that that minor structural changes of molecules could cause large changes in assembly.In addition,a series of computational calculations were conducted to verify the AP interaction between L-PF1/L-PF2 and OFN.This work demonstrated that arene-perfluoroarene interaction could drive chiral transfer,chiral amplification and chiral inversion and provided a new method for the preparation of chiroptical materials.展开更多
Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated fo...Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.展开更多
Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as pre...Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as precursors to synthesize biodegradable polymers.As an al-ternative to fossil resources,renew-able lignocellulosic biomass has been used to access chiral chemicals,due to the versatile inherent stere-ostructures and multiple functional groups,such as hydroxyl,carbonyl,and phenyl ether groups.Typically,as the two main units of(hemi)cel-lulose components in lignocellulosic biomass,D-xylose and D-glucose bear multiple chiral centers(e.g.,2R-3S-4R for D-xylose and 2R-3S-4R-5R for D-glucose).Lignin bearsβ-O-4 linkages,exhibiting(R,S/S,R)or(R,R/S,S)stereocenters at the side-chainαandβcarbon atoms.The valorization of biomass into optical-ly pure chiral chemicals is vital for developing a more sustainable future.This review discuss-es the production of typical chiral chemicals derived from biomass through chemocatalysis,including lactones(e.g.,R/S-valerolactone),carboxylic acids(e.g.,D/L-glyceric acid,D/L-lactic acid),polyols(e.g.,tetrose),furans,oligosaccharides,and others.Two strategies are generally employed.One approach involves first producing achiral platform chemicals from biomass,followed by the introduction of asymmetric catalysts to reconstruct stereocenters.The second relates to selectively preserving one or more inherent stereocenters in the natural biomass structure during complex cascade reactions in which biomass feedstock acts as a“chi-ral pool",thus eliminating the establishment of stereocenter.The feedstock,methods em-ployed,and enantioselectivity and applications of the target chiral chemicals are discussed.Despite these advances,the synthesis of optically pure chemicals from biomass is still in its in-fancy.The coming decade presents both extraordinary challenges and opportunities in biomass-derived chiral chemistry.Future research should be focused on:(1)integrating well-established asymmetric catalysis techniques and methods with biomass’s inherent chiral pools,presenting an unprecedented opportunity to expand the chemical space of sustainable chiral compounds;(2)mastering polyfunctional complexity of chiral chemicals through holis-tic utilization of biomass’multichiral centers;(3)unlocking lignin’s stereochemical treasury that represents the next frontier in biomass valorization.展开更多
Albeit notable endeavors in the construction of organophosphorodithioates,the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge.Herein,an efficient orga...Albeit notable endeavors in the construction of organophosphorodithioates,the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge.Herein,an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine.This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields(up to 98 %yield) with high stereoselectivities(up to 97 % ee and >99:1 E/Z).展开更多
Tellurene,a chiral chain semiconductor with a narrow bandgap and exceptional strain sensitivity,emerges as a pivotal material for tailoring electronic and optoelectronic properties via strain engineering.This study el...Tellurene,a chiral chain semiconductor with a narrow bandgap and exceptional strain sensitivity,emerges as a pivotal material for tailoring electronic and optoelectronic properties via strain engineering.This study elucidates the fundamental mechanisms of ultrafast laser shock imprinting(LSI)in two-dimensional tellurium(Te),establishing a direct relationship between strain field orientation,mold topology,and anisotropic structural evolution.This is the first demonstration of ultrafast LSI on chiral chain Te unveiling orientation-sensitive dislocation networks.By applying controlled strain fields parallel or transverse to Te’s helical chains,we uncover two distinct deformation regimes.Strain aligned parallel to the chain’s direction induces gliding and rotation governed by weak interchain interactions,preserving covalent intrachain bonds and vibrational modes.In contrast,transverse strain drives shear-mediated multimodal deformations—tensile stretching,compression,and bending—resulting in significant lattice distortions and electronic property modulation.We discovered the critical role of mold topology on deformation:sharp-edged gratings generate localized shear forces surpassing those from homogeneous strain fields via smooth CD molds,triggering dislocation tangle formation,lattice reorientation,and inhomogeneous plastic deformation.Asymmetrical strain configurations enable localized structural transformations while retaining single-crystal integrity in adjacent regions—a balance essential for functional device integration.These insights position LSI as a precision tool for nanoscale strain engineering,capable of sculpting 2D material morphologies without compromising crystallinity.By bridging ultrafast mechanics with chiral chain material science,this work advances the design of strain-tunable devices for next-generation electronics and optoelectronics,while establishing a universal framework for manipulating anisotropic 2D systems under extreme strain rates.This work discovered crystallographic orientation-dependent deformation mechanisms in 2D Te,linking parallel strain to chain gliding and transverse strain to shear-driven multimodal distortion.It demonstrates mold geometry as a critical lever for strain localization and dislocation dynamics,with sharp-edged gratings enabling unprecedented control over lattice reorientation.Crucially,the identification of strain field conditions that reconcile severe plastic deformation with single-crystal retention offers a pathway to functional nanostructure fabrication,redefining LSI’s potential in ultrafast strain engineering of chiral chain materials.展开更多
The detection of amino acid enantiomers holds significant importance in biomedical,chemical,food,and other fields.Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensit...The detection of amino acid enantiomers holds significant importance in biomedical,chemical,food,and other fields.Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes,which can compromise accuracy and repeatability.In this study,we report a novel fluorescent probe(R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths(>60 nm).This water-soluble probe(R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers,enabling reliable chiral detection of 14 natural amino acids.It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color.Additionally,a logic operation with two inputs and three outputs was constructed based on these optical properties.Notably,amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels.This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.展开更多
In recent years,chiral inorganic nanomaterials have become promising candidates for applications in sensing,catalysis,biomedicine,and photonics.Plasmonic nanomaterials with an intrinsic chiral structure exhibit intrig...In recent years,chiral inorganic nanomaterials have become promising candidates for applications in sensing,catalysis,biomedicine,and photonics.Plasmonic nanomaterials with an intrinsic chiral structure exhibit intriguing geometry‑dependent optical chirality,which benefits the combination of plasmonic characteristics with chirality.Recent advances in the biomolecule‑directed geometric control of intrinsically chiral plasmonic nanomaterials have further provided great opportunities for their widespread applications in many emerging technological areas.In this review,we present the recent progress in biosensing using chiral inorganic nanomaterials,with a particular focus on electrochemical and enzyme‑mimicking catalytic approaches.This paper commences with a review of the basic tenets underlying chiral nanocatalysts,incorporating the chiral ligand‑induced mechanism and the architectures of intrinsically chiral nanostructures.Additionally,it methodically expounds upon the applications of chiral nanocatalysts in the realms of electrochemical biosensing and enzyme‑mimicking catalytic biosensing respectively.Conclusively,it proffers a prospective view of the hurdles and prospects that accompany the deployment of chiral nanoprobes for nascent biosensing applications.By rational design of the chiral nanoprobes,it is envisioned that biosensing with increasing sensitivity and resolution toward the single‑molecule level can be achieved,which will substantially promote sensing applications in many emerging interdisciplinary areas.展开更多
The presence of chirality,a fundamental attribute found in nature,is of great significance in the field of pharmaceutical science.Chiral drugs are unique in that their molecular structure is non-superimposable on its ...The presence of chirality,a fundamental attribute found in nature,is of great significance in the field of pharmaceutical science.Chiral drugs are unique in that their molecular structure is non-superimposable on its mirror image.This stereoisomerism significantly impacts the functionality,metabolic pathway,effectiveness,and safety of chiral medications.The enantiomers of chiral drugs can exhibit diverse pharmacological effects in the human body.As a result,it is essential to separate and purify chiral drugs effectively.Despite the abundance of reports on chiral drug separation membranes,there is a dearth of comprehensive reviews.This paper aims to fill this gap by providing a thorough review from a materials perspective,with a focus on the design and construction of chiral drug separation membranes.Furthermore,it systematically analyzes the separation mechanisms employed by these membranes.The paper also delves into the challenges and prospects related to chiral drug separation membranes,with the intention of imparting valuable insights for further research and development in this field.展开更多
The search for the chiral magnetic effect(CME) in relativistic heavy-ion collisions(HICs) is challenged by significant background contamination. We present a novel deep learning approach based on a U-Net architecture ...The search for the chiral magnetic effect(CME) in relativistic heavy-ion collisions(HICs) is challenged by significant background contamination. We present a novel deep learning approach based on a U-Net architecture to time-reversely unfold the dynamics of CME-related charge separation, enabling the reconstruction of the physics signal across the entire evolution of HICs. Trained on the events simulated by a multi-phase transport model with different cases of CME settings, our model learns to recover the charge separation based on final-state transverse momentum distributions at either the quark–gloun plasma freeze-out or hadronic freeze-out. This devises a methodological tool for the study of CME and underscores the promise of deep learning approaches in retrieving physics signals in HICs.展开更多
Chirality,a common phenomenon in nature,appears in structures ranging from galaxies and condensed matter to atomic nuclei.There is a persistent demand for new,high-precision methods to detect chiral structures,particu...Chirality,a common phenomenon in nature,appears in structures ranging from galaxies and condensed matter to atomic nuclei.There is a persistent demand for new,high-precision methods to detect chiral structures,particularly at the microscale.Here,we propose a novel method,vortex Mössbauer spectroscopy,for probing chiral structures.By leveraging the orbital angular momentum carried by vortex beams,this approach achieves high precision in detecting chiral structures at scales ranging from nanometers to hundreds of nanometers.Our simulation shows the ratio of characteristic lines in the Mössbauer spectra of ^(57)Fe under vortex beams exhibits differences of up to four orders of magnitude for atomic structures with different arrangements.Additionally,simulations reveal the response of ^(229m)Th chiral structures to vortex beams with opposite angular momenta differs by approximately 49-fold.These significant spectral variations indicate that this new vortex Mössbauer probe holds great potential for investigating the microscopic chiral structures and interactions of matter.展开更多
The simultaneous description for nuclear matter and finite nuclei has been a long-standing challenge in nuclear ab initio theory.With the success for nuclear matter,the relativistic Brueckner-Hartree-Fock(RBHF)theory ...The simultaneous description for nuclear matter and finite nuclei has been a long-standing challenge in nuclear ab initio theory.With the success for nuclear matter,the relativistic Brueckner-Hartree-Fock(RBHF)theory with covariant chiral interactions is a promising ab initio approach to describe both nuclear matter and finite nuclei.In the description of finite nuclei with the current RBHF theory,the covariant chiral interactions have to be localized to make calculations feasible.In order to examine the reliability and validity,in this letter,the RBHF theory with local and nonlocal covariant chiral interactions at leading order is applied to nuclear matter.The low-energy constants in the covariant chiral interactions determined with the local regularization are close to those with the nonlocal regularization.Moreover,the RBHF theory using covariant chiral interactions with local and nonlocal regulators provides an equally good description of the saturation properties of nuclear matter.The present work paves the way for the implementation of covariant chiral interactions in RBHF theory for finite nuclei.展开更多
Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination ...Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination chemistry, and material chemistry, which involve in many subjects including chemistry, physics, optics, medi-cine, pharmacology, biology, crystal engineering, environmental science, etc. Their special structural features such as porosity, modularity, and chirality have endowed them with a variety of unique effects in promoting enantioselective processes, particularly asymmetric catalysis. Here, we provide a brief review of the state of CMOF field from the privileged ligand design to the heterogeneous enantioselective catalysis. We hope that this review will provide researchers a better understanding of CMOF chemistry and facilitate the future research endeavors for rationally designing privileged chiral framework materials for challenging catalytic applications.展开更多
The scale mismatch between nanoscale biomolecules and sub-wavelength light hinders circular dichroism(CD)spectroscopy for chiral small molecule sensing.In this study,we propose a high quality-factor(Q-factor)optical c...The scale mismatch between nanoscale biomolecules and sub-wavelength light hinders circular dichroism(CD)spectroscopy for chiral small molecule sensing.In this study,we propose a high quality-factor(Q-factor)optical cavity that offers a breakthrough solution to the intrinsic trade-off between optical chirality density and mode loss.A spin-preserving chiral metasurface utilizes bound states in the continuum(BIC)-guided mode resonance(GMR)degenerate modes to achieve a high Q-factor,while ensuring the preservation of chirality purity for circularly polarized light propagating within the cavity via spin-locking mechanism.Experimental results demonstrate that the BIC-GMR degenerate state enables near-perfect transmission CD up to 0.99,without requiring symmetry breaking.Full-wave simulations further predict that this synergistically enhanced system can achieve a Q-factor as high as 10037 and generate a localized field in the molecular interaction region with an optical chirality density enhancement of up to 400-fold,leading to 5025-fold amplification of the CD signal.This study establishes a foundation for detecting low-concentration chiral molecules,reveals high-Q enhancement,and advances chiral toward single-molecule sensitivity,opening new research avenues in chiral biosensing.展开更多
The superchiral field that enables ultrasensitive detection and discrimination of chiral matter beyond that of circularly polarized light by its field structure has emerged as a powerful tool in chiroptical spectrosco...The superchiral field that enables ultrasensitive detection and discrimination of chiral matter beyond that of circularly polarized light by its field structure has emerged as a powerful tool in chiroptical spectroscopy,spin photonics,and analytical chemistry.Specially,the superchiral field at the wavelength beyond 15μm is indispensable for various mid-infrared applications,such as ultrasensitive chiroptical sensing in the molecular fingerprint region.Here we propose and present a new strategy to realize the superchiral field with a Kuhn’s dissymmetric factor up to∼90 at the wavelength beyond 15μm.This is enabled by the high-quality(up to∼10^(4))multipole resonance induced by Brillouin-zone-folding-driven quasi-guided mode in a diamond metasurface.This work opens up a new avenue towards realizing mid-infrared superchiral fields at the wavelength beyond 15μm.展开更多
Chiral pillar[n]arenes have shown great research value and application prospect in construction of chiral materials and chiral applications,due to their inherent planar chiral configurations,chiral recognition ability...Chiral pillar[n]arenes have shown great research value and application prospect in construction of chiral materials and chiral applications,due to their inherent planar chiral configurations,chiral recognition ability,easy modification and highly symmetric hydrophobic cavity.This review systematically summarized the conformation inversion factors of planar chiral pillar[5]arenes(pR/p S),such as solvents,temperature,substituent size,alkyl chains,chiral and achiral vip molecules.We firstly introduced the applications of chiral pillar[n]arenes for constructing chiral materials and pointed out that planar conformation inversion showed a great potential role in constructing chiral materials.Then,we mainly concluded the chiral applications of chiral and planar chiral pillar[n]arenes like chiral enantiomer analysis by circular dichroism,electrochemistry or chiral fluorescence sensing.From this review,we found that the inherent planar chiral conformation of chiral pillar[n]arenes have played a very important role in chiral field in the future.展开更多
Chirality is ubiquitous in natural world.Although with similar physical and chemical properties,chiral enantiomers could play different roles in biochemical processes.Discrimination of chiral enantiomers is extremely ...Chirality is ubiquitous in natural world.Although with similar physical and chemical properties,chiral enantiomers could play different roles in biochemical processes.Discrimination of chiral enantiomers is extremely important in biochemical,analytical chemistry,and pharmaceutical industries.Conventional chiroptical spectroscopic methods are disadvantageous at a limited detection sensitivity because of the weak signals of natural chiral molecules.Recently,superchiral fields were proposed to effectively enhance the interaction between light and molecules,allowing for ultrasensitive chiral detection.Intensive theoretical and experimental works have been devoted to generation of superchiral fields based on artificial nanostructures and their application in ultrasensitive chiral sensing.In this review,we present a survey on these works.We begin with the introduction of chiral properties of electromagnetic fields.Then,the optical chirality enhancement and ultrasensitive chiral detection based on chiral and achiral nanostructures are discussed respectively.Finally,we give a short summary and a perspective for the future ultrasensitive chiral sensing.展开更多
Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded...Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded organic frameworks(HOFs)have promising application potential for embedding enzymes.In fact,no metal involvement is required,and HOFs exhibit superior biocompatibility,and free access to substrates in mesoporous channels.Herein,a facile in situ growth approach was proposed for the self-assembly of alcohol dehydrogenase encapsulated in HOF.The micron-scale bio-catalytic composite was rapidly synthesized under mild conditions(aqueous phase and ambient temperature)with a controllable embedding rate.The high crystallinity and periodic arrangement channels of HOF were preserved at a high enzyme encapsulation efficiency of 59%.This bio-composite improved the tolerance of the enzyme to the acid-base environment and retained 81%of its initial activity after five cycles of batch hydrogenation involving NADH coenzyme.Based on this controllably synthesized bio-catalytic material and a common lipase,we further developed a two-stage cascade microchemical system and achieved the continuous production of chiral hydroxybutyric acid(R-3-HBA).展开更多
A series of optically active copolymers with various feed ratios have been synthesized through helix-sense-selective copolymerization catalyzed by[Rh(norbornadiene)Cl]2-triethylamine.This process involves two proline-...A series of optically active copolymers with various feed ratios have been synthesized through helix-sense-selective copolymerization catalyzed by[Rh(norbornadiene)Cl]2-triethylamine.This process involves two proline-derived acetylene monomers,(S)-N-(4-chlorophenyl)carbamoyl-2-ethynyl pyrrolidine(MCl)and(S)-N-(tert-butoxycarbonyl)-2-ethynyl pyrrolidine,followed by acidic deprotection and neutralization.These copolymers adopt helical conformations with a preferred handedness,as demonstrated by nuclear magnetic resonance spectroscopy and a series of spectroscopic analyses.The chiroptical activity intensity of copolymer has been found to increase with MCl content.Consequently,the enantioseparation capabilities of copolymers containing 95 mol%,90 mol%,and 85 mol%MCl units have been assessed as chiral stationary phases in high-performance liquid chromatography because of their good chiroptical activities.These chiral stationary phases effectively enantioseparate racemic alcohols,sulfoxides,amides,and metal complexes.Notably,the copolymer with 90 mol%MCl shows superior chiral recognition ability,especially for 1-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl)ethanol(α=1.19)and 4-methylbenzenesulfinamide(α=1.47).Insights from molecular dynamic simulation and autodock analysis indicate that hydrogen bonding andπ-πstacking interactions between the chiral stationary phases and enantiomers play a key role for successful chiral separation.Our contribution not only demonstrates the importance of hydrogen bonding donor and copolymer chiroptical activity of chiral stationary phases for chiral resolution,but will also provide valuable insights for the future development of novel stationary phases.展开更多
The catalytic enantioselective electrophilic amination reaction has emerged as a highly efficient method for synthesizing diverse nitrogen-containing chiral molecules,with the development of various asymmetric catalys...The catalytic enantioselective electrophilic amination reaction has emerged as a highly efficient method for synthesizing diverse nitrogen-containing chiral molecules,with the development of various asymmetric catalysis systems.Chiral phosphoric acids(CPA)have been widely acknowledged as versatile chiral organocatalysts since it was first discovered in 2004,finding application in catalyzing diverse asymmetric reactions.A comprehensive overview of recent advances in CPA-catalyzed asymmetric electrophilic amination reactions using different N-electrophilic reagents,including azo reagents,aryldiazonium salts,and imine derivatives,is presented.Furthermore,insights into future developments in this field are offered.展开更多
Atropisomeric phosphines are crucial for asymmetric catalysis but remain synthetically challenging.Herein,an N-heterocyclic carbene(NHC)catalyzed esterification reaction of dialdehydes with arylboronic acids was devel...Atropisomeric phosphines are crucial for asymmetric catalysis but remain synthetically challenging.Herein,an N-heterocyclic carbene(NHC)catalyzed esterification reaction of dialdehydes with arylboronic acids was developed,successfully constructing the framework of axially chiral phosphorus compounds.Mechanistic studies have revealed that the reaction initially undergoes a desymmetrization process,followed by a kinetic resolution pathway,affording a series of axially chiral phosphorus compounds with high enantioselectivity(up to 92%ee).展开更多
基金financially supported by the National Natural Science Foundation of China (Nos.22171165 and 22371170)Natural Science Foundation of Shandong Province (No.ZR2022MB080)Scientific and Technological Frontiers in Project of Henan Province(No.242102110192)。
文摘Co-assembling chiral molecules with achiral compounds via non-covalent interactions like areneperfluoroarene(AP) interactions offers an effective approach for fabricating chiral functional materials.Herein,chiral molecules L/D-PF1 and L/D-PF2 with pyrene groups were synthesized and its chiroptical properties upon co-assembly with achiral compound octafluoronaphthalene(OFN) through AP interaction were systemically studied.The co-assembly of L/D-PF1/OFN and L/D-PF2/OFN exhibited distinct chiroptical properties such as circular dichroism(CD) and circularly polarized luminescence(CPL) signals.Chirality transfer from the chirality center of L/D-PF1 and L/D-PF2 to the achiral OFN and chiral amplification were successfully achieved.Besides,no significant CPL signal was observed in the self-assembly of L/DPF1 or L/D-PF2 while co-assembly with OFN exhibited obvious CPL amplification induced by AP interaction.Notably,a reversal CD signal and CPL signal could be observed in L/D-PF2/OFN when the molar ratio changed from 1:1 to 1:2 while not found in L/D-PF1/OFN,indicating that that minor structural changes of molecules could cause large changes in assembly.In addition,a series of computational calculations were conducted to verify the AP interaction between L-PF1/L-PF2 and OFN.This work demonstrated that arene-perfluoroarene interaction could drive chiral transfer,chiral amplification and chiral inversion and provided a new method for the preparation of chiroptical materials.
基金supported by the National Natural Science Foundation of China (Nos.22064020,22364022,and 22174125)the Applied Basic Research Foundation of Yunnan Province (Nos.202101AT070101 and 202201AT070029)。
文摘Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.
基金supported by the National Natural Sci-ence Foundation of China(Nos.22478263,22308230)Natural Science Foundation of Sichuan(No.2024NSF-SC1134)+2 种基金China Postdoctoral Science Foundation(No.2024T170612)111 center(B17030)the Fun-damental Research Funds for the Central Universities.
文摘Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as precursors to synthesize biodegradable polymers.As an al-ternative to fossil resources,renew-able lignocellulosic biomass has been used to access chiral chemicals,due to the versatile inherent stere-ostructures and multiple functional groups,such as hydroxyl,carbonyl,and phenyl ether groups.Typically,as the two main units of(hemi)cel-lulose components in lignocellulosic biomass,D-xylose and D-glucose bear multiple chiral centers(e.g.,2R-3S-4R for D-xylose and 2R-3S-4R-5R for D-glucose).Lignin bearsβ-O-4 linkages,exhibiting(R,S/S,R)or(R,R/S,S)stereocenters at the side-chainαandβcarbon atoms.The valorization of biomass into optical-ly pure chiral chemicals is vital for developing a more sustainable future.This review discuss-es the production of typical chiral chemicals derived from biomass through chemocatalysis,including lactones(e.g.,R/S-valerolactone),carboxylic acids(e.g.,D/L-glyceric acid,D/L-lactic acid),polyols(e.g.,tetrose),furans,oligosaccharides,and others.Two strategies are generally employed.One approach involves first producing achiral platform chemicals from biomass,followed by the introduction of asymmetric catalysts to reconstruct stereocenters.The second relates to selectively preserving one or more inherent stereocenters in the natural biomass structure during complex cascade reactions in which biomass feedstock acts as a“chi-ral pool",thus eliminating the establishment of stereocenter.The feedstock,methods em-ployed,and enantioselectivity and applications of the target chiral chemicals are discussed.Despite these advances,the synthesis of optically pure chemicals from biomass is still in its in-fancy.The coming decade presents both extraordinary challenges and opportunities in biomass-derived chiral chemistry.Future research should be focused on:(1)integrating well-established asymmetric catalysis techniques and methods with biomass’s inherent chiral pools,presenting an unprecedented opportunity to expand the chemical space of sustainable chiral compounds;(2)mastering polyfunctional complexity of chiral chemicals through holis-tic utilization of biomass’multichiral centers;(3)unlocking lignin’s stereochemical treasury that represents the next frontier in biomass valorization.
基金financial support from Natural Science Foundation of China (No.22161005)Guangxi Natural Science Foundation (Nos.2021GXNSFDA075005,2024GXNSFFA010001)。
文摘Albeit notable endeavors in the construction of organophosphorodithioates,the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge.Herein,an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine.This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields(up to 98 %yield) with high stereoselectivities(up to 97 % ee and >99:1 E/Z).
基金financial support from NSF ExpandQISE program.The synthesis of tellurene was supported by NSF under grant no.CMMI-2046936supports from Purdue Research Foundation.
文摘Tellurene,a chiral chain semiconductor with a narrow bandgap and exceptional strain sensitivity,emerges as a pivotal material for tailoring electronic and optoelectronic properties via strain engineering.This study elucidates the fundamental mechanisms of ultrafast laser shock imprinting(LSI)in two-dimensional tellurium(Te),establishing a direct relationship between strain field orientation,mold topology,and anisotropic structural evolution.This is the first demonstration of ultrafast LSI on chiral chain Te unveiling orientation-sensitive dislocation networks.By applying controlled strain fields parallel or transverse to Te’s helical chains,we uncover two distinct deformation regimes.Strain aligned parallel to the chain’s direction induces gliding and rotation governed by weak interchain interactions,preserving covalent intrachain bonds and vibrational modes.In contrast,transverse strain drives shear-mediated multimodal deformations—tensile stretching,compression,and bending—resulting in significant lattice distortions and electronic property modulation.We discovered the critical role of mold topology on deformation:sharp-edged gratings generate localized shear forces surpassing those from homogeneous strain fields via smooth CD molds,triggering dislocation tangle formation,lattice reorientation,and inhomogeneous plastic deformation.Asymmetrical strain configurations enable localized structural transformations while retaining single-crystal integrity in adjacent regions—a balance essential for functional device integration.These insights position LSI as a precision tool for nanoscale strain engineering,capable of sculpting 2D material morphologies without compromising crystallinity.By bridging ultrafast mechanics with chiral chain material science,this work advances the design of strain-tunable devices for next-generation electronics and optoelectronics,while establishing a universal framework for manipulating anisotropic 2D systems under extreme strain rates.This work discovered crystallographic orientation-dependent deformation mechanisms in 2D Te,linking parallel strain to chain gliding and transverse strain to shear-driven multimodal distortion.It demonstrates mold geometry as a critical lever for strain localization and dislocation dynamics,with sharp-edged gratings enabling unprecedented control over lattice reorientation.Crucially,the identification of strain field conditions that reconcile severe plastic deformation with single-crystal retention offers a pathway to functional nanostructure fabrication,redefining LSI’s potential in ultrafast strain engineering of chiral chain materials.
基金the financial support from the National Natural Science Foundation of China(Nos.22377097,22307036,22074114)Natural Science Foundation of Hubei Province of China(Nos.2020CFB623,2021CFB556)Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education(No.LCX202305)。
文摘The detection of amino acid enantiomers holds significant importance in biomedical,chemical,food,and other fields.Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes,which can compromise accuracy and repeatability.In this study,we report a novel fluorescent probe(R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths(>60 nm).This water-soluble probe(R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers,enabling reliable chiral detection of 14 natural amino acids.It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color.Additionally,a logic operation with two inputs and three outputs was constructed based on these optical properties.Notably,amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels.This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.
文摘In recent years,chiral inorganic nanomaterials have become promising candidates for applications in sensing,catalysis,biomedicine,and photonics.Plasmonic nanomaterials with an intrinsic chiral structure exhibit intriguing geometry‑dependent optical chirality,which benefits the combination of plasmonic characteristics with chirality.Recent advances in the biomolecule‑directed geometric control of intrinsically chiral plasmonic nanomaterials have further provided great opportunities for their widespread applications in many emerging technological areas.In this review,we present the recent progress in biosensing using chiral inorganic nanomaterials,with a particular focus on electrochemical and enzyme‑mimicking catalytic approaches.This paper commences with a review of the basic tenets underlying chiral nanocatalysts,incorporating the chiral ligand‑induced mechanism and the architectures of intrinsically chiral nanostructures.Additionally,it methodically expounds upon the applications of chiral nanocatalysts in the realms of electrochemical biosensing and enzyme‑mimicking catalytic biosensing respectively.Conclusively,it proffers a prospective view of the hurdles and prospects that accompany the deployment of chiral nanoprobes for nascent biosensing applications.By rational design of the chiral nanoprobes,it is envisioned that biosensing with increasing sensitivity and resolution toward the single‑molecule level can be achieved,which will substantially promote sensing applications in many emerging interdisciplinary areas.
基金supported by the Foundation Research Project of Kaili University(No.2025ZD007)the National Key Research and Development Program of China(No.2021YFB3801503)the Joint Research Program of Shaoxing University and Shaoxing Institute,Zhejiang University(No.2023LHLG006),China.
文摘The presence of chirality,a fundamental attribute found in nature,is of great significance in the field of pharmaceutical science.Chiral drugs are unique in that their molecular structure is non-superimposable on its mirror image.This stereoisomerism significantly impacts the functionality,metabolic pathway,effectiveness,and safety of chiral medications.The enantiomers of chiral drugs can exhibit diverse pharmacological effects in the human body.As a result,it is essential to separate and purify chiral drugs effectively.Despite the abundance of reports on chiral drug separation membranes,there is a dearth of comprehensive reviews.This paper aims to fill this gap by providing a thorough review from a materials perspective,with a focus on the design and construction of chiral drug separation membranes.Furthermore,it systematically analyzes the separation mechanisms employed by these membranes.The paper also delves into the challenges and prospects related to chiral drug separation membranes,with the intention of imparting valuable insights for further research and development in this field.
基金supported by the National Natural Science Foundation of China (Grant Nos.12147101 and 12325507)the National Key Research and Development Program of China (Grant No.2022YFA1604900)+4 种基金the Guangdong Major Project of Basic and Applied Basic Research (Grant No.2020B0301030008 for S.G.and G.M.)the CUHK-Shenzhen university development fund (Grant Nos.UDF01003041 and UDF03003041)Shenzhen Peacock Fund (Grant No.2023TC0179 for K.Z.)the RIKEN TRIP initiative (RIKEN Quantum),JSPS KAKENHI (Grant No.25H01560)JST-BOOST (Grant No.JPMJBY24H9 for L.W.)。
文摘The search for the chiral magnetic effect(CME) in relativistic heavy-ion collisions(HICs) is challenged by significant background contamination. We present a novel deep learning approach based on a U-Net architecture to time-reversely unfold the dynamics of CME-related charge separation, enabling the reconstruction of the physics signal across the entire evolution of HICs. Trained on the events simulated by a multi-phase transport model with different cases of CME settings, our model learns to recover the charge separation based on final-state transverse momentum distributions at either the quark–gloun plasma freeze-out or hadronic freeze-out. This devises a methodological tool for the study of CME and underscores the promise of deep learning approaches in retrieving physics signals in HICs.
基金supported in part by the National Key R&D Program(Grant No.2023YFA1606900)the National Natural Science Foundation of China(Grant No.12235003)。
文摘Chirality,a common phenomenon in nature,appears in structures ranging from galaxies and condensed matter to atomic nuclei.There is a persistent demand for new,high-precision methods to detect chiral structures,particularly at the microscale.Here,we propose a novel method,vortex Mössbauer spectroscopy,for probing chiral structures.By leveraging the orbital angular momentum carried by vortex beams,this approach achieves high precision in detecting chiral structures at scales ranging from nanometers to hundreds of nanometers.Our simulation shows the ratio of characteristic lines in the Mössbauer spectra of ^(57)Fe under vortex beams exhibits differences of up to four orders of magnitude for atomic structures with different arrangements.Additionally,simulations reveal the response of ^(229m)Th chiral structures to vortex beams with opposite angular momenta differs by approximately 49-fold.These significant spectral variations indicate that this new vortex Mössbauer probe holds great potential for investigating the microscopic chiral structures and interactions of matter.
基金supported in part by the National Natural Science Foundation of China(Grant Nos.12435006,12435007,12475117,12141501,and 123B2080)the National Key R&D Program of China(Grant No.2024YFE0109803)the National Key Laboratory of Neutron Science and Technology(Grant No.NST202401016)。
文摘The simultaneous description for nuclear matter and finite nuclei has been a long-standing challenge in nuclear ab initio theory.With the success for nuclear matter,the relativistic Brueckner-Hartree-Fock(RBHF)theory with covariant chiral interactions is a promising ab initio approach to describe both nuclear matter and finite nuclei.In the description of finite nuclei with the current RBHF theory,the covariant chiral interactions have to be localized to make calculations feasible.In order to examine the reliability and validity,in this letter,the RBHF theory with local and nonlocal covariant chiral interactions at leading order is applied to nuclear matter.The low-energy constants in the covariant chiral interactions determined with the local regularization are close to those with the nonlocal regularization.Moreover,the RBHF theory using covariant chiral interactions with local and nonlocal regulators provides an equally good description of the saturation properties of nuclear matter.The present work paves the way for the implementation of covariant chiral interactions in RBHF theory for finite nuclei.
基金the National Key R&D Program of China(2023YFA1507601)the National Natural Science Foundation of China(22522108,52373213,22301176).
文摘Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination chemistry, and material chemistry, which involve in many subjects including chemistry, physics, optics, medi-cine, pharmacology, biology, crystal engineering, environmental science, etc. Their special structural features such as porosity, modularity, and chirality have endowed them with a variety of unique effects in promoting enantioselective processes, particularly asymmetric catalysis. Here, we provide a brief review of the state of CMOF field from the privileged ligand design to the heterogeneous enantioselective catalysis. We hope that this review will provide researchers a better understanding of CMOF chemistry and facilitate the future research endeavors for rationally designing privileged chiral framework materials for challenging catalytic applications.
基金financially supported by the POSCO-POSTECH-RIST Convergence Research Center program funded by POSCOthe National Research Foundation (NRF) grant (RS-2024-00462912) funded by the Ministry of Science and ICT (MSIT) of the Korean government+4 种基金partially supported by National Natural Science Foundation of China (Nos. 12274074, 12134013)Natural Science Foundation of Jiangsu Province (BK20242024)China Scholarship Council (202406090137)Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX24_0379)the NRF Ph.D. fellowship (RS-202525437554) funded by the Ministry of Education (MOE) of the Korean government
文摘The scale mismatch between nanoscale biomolecules and sub-wavelength light hinders circular dichroism(CD)spectroscopy for chiral small molecule sensing.In this study,we propose a high quality-factor(Q-factor)optical cavity that offers a breakthrough solution to the intrinsic trade-off between optical chirality density and mode loss.A spin-preserving chiral metasurface utilizes bound states in the continuum(BIC)-guided mode resonance(GMR)degenerate modes to achieve a high Q-factor,while ensuring the preservation of chirality purity for circularly polarized light propagating within the cavity via spin-locking mechanism.Experimental results demonstrate that the BIC-GMR degenerate state enables near-perfect transmission CD up to 0.99,without requiring symmetry breaking.Full-wave simulations further predict that this synergistically enhanced system can achieve a Q-factor as high as 10037 and generate a localized field in the molecular interaction region with an optical chirality density enhancement of up to 400-fold,leading to 5025-fold amplification of the CD signal.This study establishes a foundation for detecting low-concentration chiral molecules,reveals high-Q enhancement,and advances chiral toward single-molecule sensitivity,opening new research avenues in chiral biosensing.
基金supported by the National Key R&D Program of China(Grant No.2024YFE0105200)the National Nature Science Foundation of China(Grant No.62405284)。
文摘The superchiral field that enables ultrasensitive detection and discrimination of chiral matter beyond that of circularly polarized light by its field structure has emerged as a powerful tool in chiroptical spectroscopy,spin photonics,and analytical chemistry.Specially,the superchiral field at the wavelength beyond 15μm is indispensable for various mid-infrared applications,such as ultrasensitive chiroptical sensing in the molecular fingerprint region.Here we propose and present a new strategy to realize the superchiral field with a Kuhn’s dissymmetric factor up to∼90 at the wavelength beyond 15μm.This is enabled by the high-quality(up to∼10^(4))multipole resonance induced by Brillouin-zone-folding-driven quasi-guided mode in a diamond metasurface.This work opens up a new avenue towards realizing mid-infrared superchiral fields at the wavelength beyond 15μm.
基金the financial support provided by the National Natural Science Foundation of China(Nos.21822407,21974146)the Foundation for Science and Tech Research Project of Gansu Province(No.20JR10RA052)。
文摘Chiral pillar[n]arenes have shown great research value and application prospect in construction of chiral materials and chiral applications,due to their inherent planar chiral configurations,chiral recognition ability,easy modification and highly symmetric hydrophobic cavity.This review systematically summarized the conformation inversion factors of planar chiral pillar[5]arenes(pR/p S),such as solvents,temperature,substituent size,alkyl chains,chiral and achiral vip molecules.We firstly introduced the applications of chiral pillar[n]arenes for constructing chiral materials and pointed out that planar conformation inversion showed a great potential role in constructing chiral materials.Then,we mainly concluded the chiral applications of chiral and planar chiral pillar[n]arenes like chiral enantiomer analysis by circular dichroism,electrochemistry or chiral fluorescence sensing.From this review,we found that the inherent planar chiral conformation of chiral pillar[n]arenes have played a very important role in chiral field in the future.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.91850205 and 11904021).
文摘Chirality is ubiquitous in natural world.Although with similar physical and chemical properties,chiral enantiomers could play different roles in biochemical processes.Discrimination of chiral enantiomers is extremely important in biochemical,analytical chemistry,and pharmaceutical industries.Conventional chiroptical spectroscopic methods are disadvantageous at a limited detection sensitivity because of the weak signals of natural chiral molecules.Recently,superchiral fields were proposed to effectively enhance the interaction between light and molecules,allowing for ultrasensitive chiral detection.Intensive theoretical and experimental works have been devoted to generation of superchiral fields based on artificial nanostructures and their application in ultrasensitive chiral sensing.In this review,we present a survey on these works.We begin with the introduction of chiral properties of electromagnetic fields.Then,the optical chirality enhancement and ultrasensitive chiral detection based on chiral and achiral nanostructures are discussed respectively.Finally,we give a short summary and a perspective for the future ultrasensitive chiral sensing.
基金supported by the National Key Research and Development Program of China(2019YFA0905100)the National Natural Science Foundation of China(21991102,22378227).
文摘Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded organic frameworks(HOFs)have promising application potential for embedding enzymes.In fact,no metal involvement is required,and HOFs exhibit superior biocompatibility,and free access to substrates in mesoporous channels.Herein,a facile in situ growth approach was proposed for the self-assembly of alcohol dehydrogenase encapsulated in HOF.The micron-scale bio-catalytic composite was rapidly synthesized under mild conditions(aqueous phase and ambient temperature)with a controllable embedding rate.The high crystallinity and periodic arrangement channels of HOF were preserved at a high enzyme encapsulation efficiency of 59%.This bio-composite improved the tolerance of the enzyme to the acid-base environment and retained 81%of its initial activity after five cycles of batch hydrogenation involving NADH coenzyme.Based on this controllably synthesized bio-catalytic material and a common lipase,we further developed a two-stage cascade microchemical system and achieved the continuous production of chiral hydroxybutyric acid(R-3-HBA).
基金supported by the National Natural Science Foundation of China(Nos.52273002 and 52333008)the funding of Boya Postdoctoral Fellowship at Peking University,BMS Junior Fellow Program and the National Funding Program for Postdoctoral Researchers(No.GZC20230031).
文摘A series of optically active copolymers with various feed ratios have been synthesized through helix-sense-selective copolymerization catalyzed by[Rh(norbornadiene)Cl]2-triethylamine.This process involves two proline-derived acetylene monomers,(S)-N-(4-chlorophenyl)carbamoyl-2-ethynyl pyrrolidine(MCl)and(S)-N-(tert-butoxycarbonyl)-2-ethynyl pyrrolidine,followed by acidic deprotection and neutralization.These copolymers adopt helical conformations with a preferred handedness,as demonstrated by nuclear magnetic resonance spectroscopy and a series of spectroscopic analyses.The chiroptical activity intensity of copolymer has been found to increase with MCl content.Consequently,the enantioseparation capabilities of copolymers containing 95 mol%,90 mol%,and 85 mol%MCl units have been assessed as chiral stationary phases in high-performance liquid chromatography because of their good chiroptical activities.These chiral stationary phases effectively enantioseparate racemic alcohols,sulfoxides,amides,and metal complexes.Notably,the copolymer with 90 mol%MCl shows superior chiral recognition ability,especially for 1-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl)ethanol(α=1.19)and 4-methylbenzenesulfinamide(α=1.47).Insights from molecular dynamic simulation and autodock analysis indicate that hydrogen bonding andπ-πstacking interactions between the chiral stationary phases and enantiomers play a key role for successful chiral separation.Our contribution not only demonstrates the importance of hydrogen bonding donor and copolymer chiroptical activity of chiral stationary phases for chiral resolution,but will also provide valuable insights for the future development of novel stationary phases.
文摘The catalytic enantioselective electrophilic amination reaction has emerged as a highly efficient method for synthesizing diverse nitrogen-containing chiral molecules,with the development of various asymmetric catalysis systems.Chiral phosphoric acids(CPA)have been widely acknowledged as versatile chiral organocatalysts since it was first discovered in 2004,finding application in catalyzing diverse asymmetric reactions.A comprehensive overview of recent advances in CPA-catalyzed asymmetric electrophilic amination reactions using different N-electrophilic reagents,including azo reagents,aryldiazonium salts,and imine derivatives,is presented.Furthermore,insights into future developments in this field are offered.
基金Project supported by the Natural Science Foundation of Henan Province(Nos.232300421234,252300421726)the Leading Talents in Scientific and Technological Innovation in Shangqiu(No.SQRC202212004)the Program of Ecological Environmental Protection in the Area of Old Course of Yellow River of Shangqiu Normal University。
文摘Atropisomeric phosphines are crucial for asymmetric catalysis but remain synthetically challenging.Herein,an N-heterocyclic carbene(NHC)catalyzed esterification reaction of dialdehydes with arylboronic acids was developed,successfully constructing the framework of axially chiral phosphorus compounds.Mechanistic studies have revealed that the reaction initially undergoes a desymmetrization process,followed by a kinetic resolution pathway,affording a series of axially chiral phosphorus compounds with high enantioselectivity(up to 92%ee).
