A series of new targets containing 3 chiral elements of central,orientational,and turbo chirality have been designed and synthesized asymmetrically.The absolute configurations and conformations of these types of chira...A series of new targets containing 3 chiral elements of central,orientational,and turbo chirality have been designed and synthesized asymmetrically.The absolute configurations and conformations of these types of chirality were concurrently controlled by using chiral sulfonimine auxiliary and unambiguously determined by x-ray diffraction analysis.These targets include alpha unnatural amino acid derivatives,which may play an important role for drug design,discovery,and development.Three propellers of turbo framework are covalently connected to a chiral C(sp^(3))center via C(sp^(2))-C(sp^(3))bonding along with a C-N axis,while one of them is orientated away from the same carbon chiral center.The turbo or propeller chirality is characterized by 2 types of molecular arrangements of propellers,clockwise(PPP)and counterclockwise(MMM),respectively.The turbo stereogenicity was found to depend on the center chirality of sulfonimine auxiliary instead of the chiral C(sp^(3))center,i.e.(S)-and(R)-sulfinyl centers led to the asymmetric formation of PPP-and MMM-configurations,respectively.Computational studies were conducted on relative energies for rotational barriers of a turbo target along the C-N anchor and the transition pathway between 2 enantiomers meeting our experimental observations.This work is anticipated to have a broad impact on chemical,biomedical,and materials sciences in the future.展开更多
Chirality has garnered significant attention in the scientific community since its discovery by Louis Pasteur over a century ago.It has been showing a profound impact on chemical,biomedical,and materials sciences.Sign...Chirality has garnered significant attention in the scientific community since its discovery by Louis Pasteur over a century ago.It has been showing a profound impact on chemical,biomedical,and materials sciences.Significant progress has been made in controlling molecular chirality,as evidenced by the several Nobel Prizes in chemistry awarded in this area,particularly for advancements in the asymmetric catalytic synthesis of molecules with central and axial chirality.However,the exploration of new types of chirality has been largely stagnant for more than half a century,likely due to the complexity and challenges inherent in this field.In this work,we present the discovery of a novel type of chirality—staircase chirality as inspired by the design and synthesis of unnatural amino acid derivatives.The architecture of staircase chirality is characterized by 2 symmetrical phenyl rings anchored by a naphthyl pier,with the rings asymmetrically displaced due to the influence of chiral auxiliaries at their para positions.This unique staircase chiral framework has been thoroughly characterized using spectroscopic techniques,with its absolute configuration definitively confirmed by x-ray diffraction analysis.Remarkably,one of the staircase molecules exhibits 4 distinct types of chirality:central,orientational,turbo,and staircase chirality,a combination that has not been previously documented in the literature.Computational studies using density functional theory(DFT)calculations were conducted to analyze the relative energies of individual staircase isomers,and the results are in agreement with our experimental findings.We believe that this discovery will open up a new research frontier in asymmetric synthesis and catalysis,with the potential to make a substantial impact on the fields of chemistry,medicine,and materials science.展开更多
3D chirality of sandwich type of organic molecules has been discovered.Te key element of this chirality is characterized by three layers of structures that are arranged nearly in parallel fashion with one on top and o...3D chirality of sandwich type of organic molecules has been discovered.Te key element of this chirality is characterized by three layers of structures that are arranged nearly in parallel fashion with one on top and one down from the center plane.Individual enantiomers of these molecules have been fully characterized by spectroscopies with their enantiomeric purity measured by chiral HPLC.Te absolute confguration was unambiguously assigned by X-ray difraction analysis.Tis is the frst multilayer 3D chirality reported and is anticipated to lead to a new research area of asymmetric synthesis and catalysis and to have a broad impact on chemical,medicinal,and material sciences in future.展开更多
New synthesis of multi-layer 3 D chiral molecules has been developed under novel conditions to give better outcomes.The aggregation-induced emission(AIE),UV irradiation/excitation,charge transfer(CT)and local excited(...New synthesis of multi-layer 3 D chiral molecules has been developed under novel conditions to give better outcomes.The aggregation-induced emission(AIE),UV irradiation/excitation,charge transfer(CT)and local excited(LE)ππ*transitions have been investigated on a representative individual enantiomer of pseudo C_2 asymmetry which was made possibly by differentiating moieties on phosphorous on N-phosphonyl ring of chiral sandwich framework.Meanwhile,a new tandem C–N/C–C coupling reaction was unexpectedly rendered providing a novel access to special benzo[a]carbazoles.展开更多
Comprehensive Summary A general and convenient photoredox-catalyzed acylation and alkylcyanation of MBH acetates has been established,enabling the assembly of the C(sp2)–C(sp3)bond by a nitrogen-centered radical stra...Comprehensive Summary A general and convenient photoredox-catalyzed acylation and alkylcyanation of MBH acetates has been established,enabling the assembly of the C(sp2)–C(sp3)bond by a nitrogen-centered radical strategy for the synthesis of trisubstituted alkenes in moderate to excellent chemical yields(48 examples in total).The reaction of MBH acetates with acyl(indanone)oxime esters afforded trisubstituted alkenes containing 1,4-dicarbonyl groups.Interestingly,the use of Eosin Y as a photocatalyst in the catalytic system resulted in the formation of distal cyano group-anchored trisubstituted alkenes via deconstructive functionalization of cycloketone oxime esters.Notably,these resulting 1,4-dicarbonyl compounds could be applied to late-stage transformations,providing important methods for the synthesis of dihydropyridazin-3(2H)-one.展开更多
Orientational chirality was discovered and characterized by a C(sp)-C(sp3)axis-anchored chiral center and a remotely anchored blocker.X-ray structural analysis proved that orientatiomers are stabilized by through-spac...Orientational chirality was discovered and characterized by a C(sp)-C(sp3)axis-anchored chiral center and a remotely anchored blocker.X-ray structural analysis proved that orientatiomers are stabilized by through-space functional groups,making it possible for 1 R-or S-chiral center to exhibit 3 orientational isomers simply by rotating operations.A new model system was proposed,fundamentally different from the traditional Felkin-Ahn-type or Cram-type models.In these traditional models,chiral C(sp^(3))center and blocking C(sp^(3))carbons are connected adjacently,and there exist 6 energy barriers during rotating along the C(sp^(2))-C(sp^(3))axis.In comparison,the present orientational chirality model shows that a chiral C(sp)-C(sp^(3))carbon is remotely located from a blocking group.Thus,it is focused on the steric dialog between a chiral C(sp^(3))center and a remotely anchored functional group.There exist 3 energy barriers for either(R)-or(S)-C(sp)-C(sp^(3))stereogenicity in the new model.Chiral amide auxiliary was proven to be an excellent chiral auxiliary in controlling rotations of orientatiomers to give complete stereoselectivity.The asymmetric synthesis of individual orientatiomers was conducted via multistep synthesis by taking advantage of the Suzuki-Miyaura cross-coupling and Sonogashira coupling reactions.Density functional theory computational study presented optimized conformers and relative energies for individual orientatiomers.This discovery would be anticipated to result in a new stereochemistry topic and have a broad impact on chemical,biomedical,and material sciences in the future.展开更多
Developing a general and mild approach to upgrade alcohols into high value products is a hot topic in synthetic chemistry because alcohol is one of the most abundant raw chemicals.Specifically,direct coupling and deox...Developing a general and mild approach to upgrade alcohols into high value products is a hot topic in synthetic chemistry because alcohol is one of the most abundant raw chemicals.Specifically,direct coupling and deoxygenative coupling of alcohols are the two main approaches for the functionalization of alcohols to afford structurally diverse products,and it receives considerable attention.Despite significant advances in the field,there still remains a great challenge to develop a general approach accommodating both coupling reactions,as they commonly involve distinct pathways.Herein,we report an electrochemical approach for the direct coupling and deoxygenative coupling of alcohols with fluorenones.Under paired electrolysis,this catalyst-dependent protocol gives divergent access to diols and tertiary alcohols.Moreover,the synthetic utility of 9H-fluoren-9-ol products has been demonstrated in the synthesis of organic luminophores,phenanthrol,phenanthridine,and amino alcohol.The present approach exhibits some impressive features:(a)catalystdependent selectivity;(b)excellentfunctional-group tolerance(156 examples);(c)mild conditions;and(d)good scalability(∼20 gram scale).展开更多
Comprehensive Summary Developing reactions for the synthesis of 6-6-4 and 6-4 carbocyclic scaffolds with a chiral quaternary center at the bridgehead position is highly desired,considering the existence of such skelet...Comprehensive Summary Developing reactions for the synthesis of 6-6-4 and 6-4 carbocyclic scaffolds with a chiral quaternary center at the bridgehead position is highly desired,considering the existence of such skeletons in natural products with biological activities and the potential of using these molecules for downstream studies in chemical biology and medicinal chemistry.Report here is accessing these target skeletons with high chemo-,regio-and enantio-selectivities through Pd(ll)/chiral N,N'-disulfonyl bisimidazoline(Bim)ligand-catalyzed asymmetric reaction of yne-allenones and arylboronic acids.展开更多
A new chiral aggregate-based tool for asymmetric synthesis has been developed by taking advantage of chiral aggregates of GAP(Group-Assisted Purification)reagents,N-phosphonyl imines.This tool was proven to be success...A new chiral aggregate-based tool for asymmetric synthesis has been developed by taking advantage of chiral aggregates of GAP(Group-Assisted Purification)reagents,N-phosphonyl imines.This tool was proven to be successful in the asymmetric GAP synthesis of functionalized 2,3-dihydrobenzofurans by reacting salicyl N-phosphonyl imines with dialkyl bromomalonates in various cosolvent systems.The chiral induction can be controlled by differentiating between two asymmetric directions simply by changing the ratios of cosolvents which are commonly adopted in AIE(aggregation-induced emission)systems.The formation of chiral aggregates was witnessed by a new analytical tool-aggregation-induced polarization(AIP).The present synthetic method will be broadly extended for general organic synthesis,particularly,for asymmetric synthesis and asymmetric catalysis in the future.展开更多
Conjugated polymers and oligomers have great potentials in various fields,especially in materials and biological sciences because of their intriguing electronic and optoelectronic properties.In recent years,the throug...Conjugated polymers and oligomers have great potentials in various fields,especially in materials and biological sciences because of their intriguing electronic and optoelectronic properties.In recent years,the through-space conjugation system has emerged as a new assembled pattern of multidimensional polymers.Here,a novel series of structurally condensed multicolumn/multilayer 3D polymers and oligomers have been designed and synthesized through one-pot Suzuki polycondensation(SPC).The intramolecularly stacked arrangement of polymers can be supported by either X-ray structural analysis or computational analysis.In all cases,polymers were obtained with modest to good yields,as determined by GPC and 1 H-NMR.MALDI-TOF analysis has proven the speculation of the step-growth process of this polymerization.The computational study of ab initio and DFT calculations based on trimer and pentamer models gives details of the structures and the electronic transition.Experimental results of optical and AIE research confirmed by calculation indicates that the present work would facilitate the research and applications in materials.展开更多
A novel class of polymers and oligomers of chiral folding chirality has been designed and synthesized,showing structurally compacted triple.column/multiple layer frameworks.Both uniformed and diferentiated aromatic ch...A novel class of polymers and oligomers of chiral folding chirality has been designed and synthesized,showing structurally compacted triple.column/multiple layer frameworks.Both uniformed and diferentiated aromatic chromophoric units were successfully constructed between naphthy!piers of this framework.Screening monomers,catalysts,and catalytic systems led 1o the success of asymmetric catalytic Suzuki-Miyaura polycouplings Enantio-and diastereochemistry were unambiguously determined by X-ray structural analysis and concurrently by comparison with a similar asymmetric induction by the same catalyst in the asymmetric synthesis of a chiral three layered product.The resuling chiral polymers exhibit intense fluorescence activity in a solid form and solution under speci fic wavelength irradiation.展开更多
So far,there have been 4 methods to control chirality including the use of chiral auxiliaries,reagents,solvents,and catalysts documented in literature and textbooks.Among them,asymmetric catalysts are normally divided...So far,there have been 4 methods to control chirality including the use of chiral auxiliaries,reagents,solvents,and catalysts documented in literature and textbooks.Among them,asymmetric catalysts are normally divided into homogeneous and heterogeneous catalysis.In this report,we present a new type of asymmetric control—asymmetric catalysis via chiral aggregates that would not belong to the above categories.This new strategy is represented by catalytic asymmetric dihydroxylation reaction of olefins in which chiral ligands are aggregated by taking advantage of typical aggregation-induced emission systems containing tetrahydrofuran and H_(2)O cosolvents.It was proven that the chiral induction can be enhanced from er of 78:22 to 97:3 simply by changing the ratios of these 2 cosolvents.展开更多
基金support from Robert A.Welch Foundation[D-1361-20210327,USA(G.L.),D-2108-20220331(R.L.))the National Natural Science Foundation of China(nos.22071102 and 91956110).
文摘A series of new targets containing 3 chiral elements of central,orientational,and turbo chirality have been designed and synthesized asymmetrically.The absolute configurations and conformations of these types of chirality were concurrently controlled by using chiral sulfonimine auxiliary and unambiguously determined by x-ray diffraction analysis.These targets include alpha unnatural amino acid derivatives,which may play an important role for drug design,discovery,and development.Three propellers of turbo framework are covalently connected to a chiral C(sp^(3))center via C(sp^(2))-C(sp^(3))bonding along with a C-N axis,while one of them is orientated away from the same carbon chiral center.The turbo or propeller chirality is characterized by 2 types of molecular arrangements of propellers,clockwise(PPP)and counterclockwise(MMM),respectively.The turbo stereogenicity was found to depend on the center chirality of sulfonimine auxiliary instead of the chiral C(sp^(3))center,i.e.(S)-and(R)-sulfinyl centers led to the asymmetric formation of PPP-and MMM-configurations,respectively.Computational studies were conducted on relative energies for rotational barriers of a turbo target along the C-N anchor and the transition pathway between 2 enantiomers meeting our experimental observations.This work is anticipated to have a broad impact on chemical,biomedical,and materials sciences in the future.
基金support from the Robert A.Welch Foundation[D-1361-20210327,USA(G.L.)and D-2108-20220331(R.L.)]the National Natural Science Foundation of China(Nos.22071102 and 91956110).
文摘Chirality has garnered significant attention in the scientific community since its discovery by Louis Pasteur over a century ago.It has been showing a profound impact on chemical,biomedical,and materials sciences.Significant progress has been made in controlling molecular chirality,as evidenced by the several Nobel Prizes in chemistry awarded in this area,particularly for advancements in the asymmetric catalytic synthesis of molecules with central and axial chirality.However,the exploration of new types of chirality has been largely stagnant for more than half a century,likely due to the complexity and challenges inherent in this field.In this work,we present the discovery of a novel type of chirality—staircase chirality as inspired by the design and synthesis of unnatural amino acid derivatives.The architecture of staircase chirality is characterized by 2 symmetrical phenyl rings anchored by a naphthyl pier,with the rings asymmetrically displaced due to the influence of chiral auxiliaries at their para positions.This unique staircase chiral framework has been thoroughly characterized using spectroscopic techniques,with its absolute configuration definitively confirmed by x-ray diffraction analysis.Remarkably,one of the staircase molecules exhibits 4 distinct types of chirality:central,orientational,turbo,and staircase chirality,a combination that has not been previously documented in the literature.Computational studies using density functional theory(DFT)calculations were conducted to analyze the relative energies of individual staircase isomers,and the results are in agreement with our experimental findings.We believe that this discovery will open up a new research frontier in asymmetric synthesis and catalysis,with the potential to make a substantial impact on the fields of chemistry,medicine,and materials science.
基金We would like to acknowledge the fnancial support from the National Natural Science Foundation of China(nos.2133200521672100)Robert A.Welch Foundation(D-1361,USA).We thank Drs.Qun Li,Yanrong Li,Wenxu Zhou,and Yi-Long Zhu and Profs Bo Jiang,Tao Jiang,and Haibo Ge for the technique assistance and helpful discussion.
文摘3D chirality of sandwich type of organic molecules has been discovered.Te key element of this chirality is characterized by three layers of structures that are arranged nearly in parallel fashion with one on top and one down from the center plane.Individual enantiomers of these molecules have been fully characterized by spectroscopies with their enantiomeric purity measured by chiral HPLC.Te absolute confguration was unambiguously assigned by X-ray difraction analysis.Tis is the frst multilayer 3D chirality reported and is anticipated to lead to a new research area of asymmetric synthesis and catalysis and to have a broad impact on chemical,medicinal,and material sciences in future.
基金supported by the National Natural Science Foundation of China(91956110,21672100)Robert A.Welch Foundation(D-1361,USA)+1 种基金financial support from Beijing National Laboratory for Molecular Sciences(BNLMS201910)support from the School of Pharmaceutical Science and Technology(SPST),Tianjin University,Tianjin,China。
文摘New synthesis of multi-layer 3 D chiral molecules has been developed under novel conditions to give better outcomes.The aggregation-induced emission(AIE),UV irradiation/excitation,charge transfer(CT)and local excited(LE)ππ*transitions have been investigated on a representative individual enantiomer of pseudo C_2 asymmetry which was made possibly by differentiating moieties on phosphorous on N-phosphonyl ring of chiral sandwich framework.Meanwhile,a new tandem C–N/C–C coupling reaction was unexpectedly rendered providing a novel access to special benzo[a]carbazoles.
基金the school level research projects of Changzhou University(No.ZMF23020007).
文摘Comprehensive Summary A general and convenient photoredox-catalyzed acylation and alkylcyanation of MBH acetates has been established,enabling the assembly of the C(sp2)–C(sp3)bond by a nitrogen-centered radical strategy for the synthesis of trisubstituted alkenes in moderate to excellent chemical yields(48 examples in total).The reaction of MBH acetates with acyl(indanone)oxime esters afforded trisubstituted alkenes containing 1,4-dicarbonyl groups.Interestingly,the use of Eosin Y as a photocatalyst in the catalytic system resulted in the formation of distal cyano group-anchored trisubstituted alkenes via deconstructive functionalization of cycloketone oxime esters.Notably,these resulting 1,4-dicarbonyl compounds could be applied to late-stage transformations,providing important methods for the synthesis of dihydropyridazin-3(2H)-one.
基金supportfrom the Robert A.Welch Foundation(D-1361-20210327,USA)from the National Natural Science Foundation ofChina(nos.22071102,91956110,22073043,and 21833002).
文摘Orientational chirality was discovered and characterized by a C(sp)-C(sp3)axis-anchored chiral center and a remotely anchored blocker.X-ray structural analysis proved that orientatiomers are stabilized by through-space functional groups,making it possible for 1 R-or S-chiral center to exhibit 3 orientational isomers simply by rotating operations.A new model system was proposed,fundamentally different from the traditional Felkin-Ahn-type or Cram-type models.In these traditional models,chiral C(sp^(3))center and blocking C(sp^(3))carbons are connected adjacently,and there exist 6 energy barriers during rotating along the C(sp^(2))-C(sp^(3))axis.In comparison,the present orientational chirality model shows that a chiral C(sp)-C(sp^(3))carbon is remotely located from a blocking group.Thus,it is focused on the steric dialog between a chiral C(sp^(3))center and a remotely anchored functional group.There exist 3 energy barriers for either(R)-or(S)-C(sp)-C(sp^(3))stereogenicity in the new model.Chiral amide auxiliary was proven to be an excellent chiral auxiliary in controlling rotations of orientatiomers to give complete stereoselectivity.The asymmetric synthesis of individual orientatiomers was conducted via multistep synthesis by taking advantage of the Suzuki-Miyaura cross-coupling and Sonogashira coupling reactions.Density functional theory computational study presented optimized conformers and relative energies for individual orientatiomers.This discovery would be anticipated to result in a new stereochemistry topic and have a broad impact on chemical,biomedical,and material sciences in the future.
基金the National Natural Science Foundation of China(grant nos.21702113,92061110,22071102,and 91956110)Anhui University(grant no.S020318006/069)the National Science Foundation(grant no.CHE-1554906)for their financial support.
文摘Developing a general and mild approach to upgrade alcohols into high value products is a hot topic in synthetic chemistry because alcohol is one of the most abundant raw chemicals.Specifically,direct coupling and deoxygenative coupling of alcohols are the two main approaches for the functionalization of alcohols to afford structurally diverse products,and it receives considerable attention.Despite significant advances in the field,there still remains a great challenge to develop a general approach accommodating both coupling reactions,as they commonly involve distinct pathways.Herein,we report an electrochemical approach for the direct coupling and deoxygenative coupling of alcohols with fluorenones.Under paired electrolysis,this catalyst-dependent protocol gives divergent access to diols and tertiary alcohols.Moreover,the synthetic utility of 9H-fluoren-9-ol products has been demonstrated in the synthesis of organic luminophores,phenanthrol,phenanthridine,and amino alcohol.The present approach exhibits some impressive features:(a)catalystdependent selectivity;(b)excellentfunctional-group tolerance(156 examples);(c)mild conditions;and(d)good scalability(∼20 gram scale).
基金We are grateful for financial support from the NSFC(Nos.21871112,21971090,and 21933003).
文摘Comprehensive Summary Developing reactions for the synthesis of 6-6-4 and 6-4 carbocyclic scaffolds with a chiral quaternary center at the bridgehead position is highly desired,considering the existence of such skeletons in natural products with biological activities and the potential of using these molecules for downstream studies in chemical biology and medicinal chemistry.Report here is accessing these target skeletons with high chemo-,regio-and enantio-selectivities through Pd(ll)/chiral N,N'-disulfonyl bisimidazoline(Bim)ligand-catalyzed asymmetric reaction of yne-allenones and arylboronic acids.
基金We would like to acknowledge the financial support from the Welch Foundation(D-1361-20210327,USA)the National Natural Science Foundation of China(Nos.22071102 and 91956110).
文摘A new chiral aggregate-based tool for asymmetric synthesis has been developed by taking advantage of chiral aggregates of GAP(Group-Assisted Purification)reagents,N-phosphonyl imines.This tool was proven to be successful in the asymmetric GAP synthesis of functionalized 2,3-dihydrobenzofurans by reacting salicyl N-phosphonyl imines with dialkyl bromomalonates in various cosolvent systems.The chiral induction can be controlled by differentiating between two asymmetric directions simply by changing the ratios of cosolvents which are commonly adopted in AIE(aggregation-induced emission)systems.The formation of chiral aggregates was witnessed by a new analytical tool-aggregation-induced polarization(AIP).The present synthetic method will be broadly extended for general organic synthesis,particularly,for asymmetric synthesis and asymmetric catalysis in the future.
基金supported by the Welch Foundation(D-1361,USA)the National Natural Science Foundation of China(22071102 and 91956110)。
文摘Conjugated polymers and oligomers have great potentials in various fields,especially in materials and biological sciences because of their intriguing electronic and optoelectronic properties.In recent years,the through-space conjugation system has emerged as a new assembled pattern of multidimensional polymers.Here,a novel series of structurally condensed multicolumn/multilayer 3D polymers and oligomers have been designed and synthesized through one-pot Suzuki polycondensation(SPC).The intramolecularly stacked arrangement of polymers can be supported by either X-ray structural analysis or computational analysis.In all cases,polymers were obtained with modest to good yields,as determined by GPC and 1 H-NMR.MALDI-TOF analysis has proven the speculation of the step-growth process of this polymerization.The computational study of ab initio and DFT calculations based on trimer and pentamer models gives details of the structures and the electronic transition.Experimental results of optical and AIE research confirmed by calculation indicates that the present work would facilitate the research and applications in materials.
基金supported by the Robert A.Welch Foundation(D-1361-20210327,USA)the National Natural Science Foundation of China(22071102 and 91956110).We thank Yangxue Liu and Liulei Ma for their synthesis assistance+1 种基金Prof.K.Hutchins and Mr.Q-X.Zheng for their assistance on GPC analysisand Prof.Y.Mechref,Dr.X.Gong,and Dr.M.Zabet for their assistance on the MALDI-TOF analysis.We thank Prof Andrei Yudin for helpful discussion.
文摘A novel class of polymers and oligomers of chiral folding chirality has been designed and synthesized,showing structurally compacted triple.column/multiple layer frameworks.Both uniformed and diferentiated aromatic chromophoric units were successfully constructed between naphthy!piers of this framework.Screening monomers,catalysts,and catalytic systems led 1o the success of asymmetric catalytic Suzuki-Miyaura polycouplings Enantio-and diastereochemistry were unambiguously determined by X-ray structural analysis and concurrently by comparison with a similar asymmetric induction by the same catalyst in the asymmetric synthesis of a chiral three layered product.The resuling chiral polymers exhibit intense fluorescence activity in a solid form and solution under speci fic wavelength irradiation.
基金financial support from Robert A.Welch Foundation(D-1361-20210327,USA)the National Natural Science Foundation of China(nos.22071102 and 91956110).
文摘So far,there have been 4 methods to control chirality including the use of chiral auxiliaries,reagents,solvents,and catalysts documented in literature and textbooks.Among them,asymmetric catalysts are normally divided into homogeneous and heterogeneous catalysis.In this report,we present a new type of asymmetric control—asymmetric catalysis via chiral aggregates that would not belong to the above categories.This new strategy is represented by catalytic asymmetric dihydroxylation reaction of olefins in which chiral ligands are aggregated by taking advantage of typical aggregation-induced emission systems containing tetrahydrofuran and H_(2)O cosolvents.It was proven that the chiral induction can be enhanced from er of 78:22 to 97:3 simply by changing the ratios of these 2 cosolvents.
