N,O-Spiroaminals have potential biological activities and abilities to modulate the physicochemical and pharmacokinetic properties of drug molecules.However,effective catalytic methods for the efficient construction o...N,O-Spiroaminals have potential biological activities and abilities to modulate the physicochemical and pharmacokinetic properties of drug molecules.However,effective catalytic methods for the efficient construction of N,O-spiroaminals are still limited to date.Herein,we report a novel 1,1,2-trifunctionalization of unactivated alkenes to rapidly and efficiently obtain a diverse array of architecturally intriguing N,O-spiroaminals.This methodology exhibits broad substrate scope,good functional group compatibility,and potential synthetic utility by a scale-up reaction,diverse product derivatizations and late-stage functionalization of complex biorelevant molecule.Notably,this transformation selectively allows for the formation of three new chemical bonds(C–O,C–C,and C–N)and one spiro quaternary carbon center across C-C double bonds.展开更多
Main observation and conclusion Herein,we report a highly chemo-and regioselective vicinal trifunctionalization of aryl iodides by palladium/norbornene(Pd/NBE)catalysis.The key feature of this new method is the introd...Main observation and conclusion Herein,we report a highly chemo-and regioselective vicinal trifunctionalization of aryl iodides by palladium/norbornene(Pd/NBE)catalysis.The key feature of this new method is the introduction of two distinct nitrogen and carbon electrophiles,with a large gap in reactivity,for ortho-unsubstituted aryl iodides via an intermolecular and intramolecular C―H functionalization,respectively.Eight types of ipso terminations can be coupled with both ortho-amination and ortho-alkylation,affording a variety of polysubstituted benzoheterocyclic scaffolds.Silicon-tethered substrates can lead to polyfucntional arenes via a single-step operation.Noteworthy,these products exhibit full-color-tunable strong fluorescence emissions with large Stokes shifts,and product 7r can serve as a fluorescent probe to specifically target lysosome in living cells.展开更多
The first Cu-catalyzed 1,2,5-trifunctionalization of abundant terminal alkynes is realized by merging hydrogen atom transfer and traceless directing strategy with SR as a transient group,delivering highly functionaliz...The first Cu-catalyzed 1,2,5-trifunctionalization of abundant terminal alkynes is realized by merging hydrogen atom transfer and traceless directing strategy with SR as a transient group,delivering highly functionalized aldehydes in moderate to excellent yields with broad substrate scope.The synthetic utility of this method was demonstrated by the gram-scale reaction and downstream transformations of the resultant products.Given the high efficient installation of three different functional groups in a single reaction,it can serve as a very attractive method for rapidly assembling complex molecules from readily available starting materials.展开更多
Functionalized bisboryl compounds have recently emerged as a new class of synthetically useful building blocks in organic synthesis.Herein,we report an efficient strategy to synthesizeβ-geminal-diboryl ketones enable...Functionalized bisboryl compounds have recently emerged as a new class of synthetically useful building blocks in organic synthesis.Herein,we report an efficient strategy to synthesizeβ-geminal-diboryl ketones enabled by a Cu/Pd-catalyzed borocarbonylative trifunctionalization of readily available alkynes and allenes.This reaction promises to be a useful method for the synthesis of functionalizedβ-geminal-diboryl ketones with broad functional group tolerance.Mechanistic studies suggest that the reaction proceeds through borocarbonylation/hydroboration cascade of both alkynes and allenes.展开更多
Carbon dioxide reduction, as a sustainable and versatile strategy for the access of chemical fuels, has attracted increasing attention and enormous efforts have been devoted to it in recent years. However, employing c...Carbon dioxide reduction, as a sustainable and versatile strategy for the access of chemical fuels, has attracted increasing attention and enormous efforts have been devoted to it in recent years. However, employing carbon dioxide as double synthons via bimolecular reduction remains challenging. Here, by leveraging the bimolecular reduction of carbon dioxide to carbonyl and methyl respectively, we describe a Pd-catalyzed trifunctionalization of alkynes with aryl iodide for the first time and showcase its advantages on the formation of various β-diketones and their application in the constructing of heterocyclic compounds with important biological activity, including pyrimidine, oxazole, pyrazole.展开更多
Trifluoromethyl carbyne(CF_(3)?:),with its three non-bonded electrons,has the potential to form three new chemical bonds.Herein,we explore a novel photocatalytic trifunctionalization of trifluoromethyl carbyne to synt...Trifluoromethyl carbyne(CF_(3)?:),with its three non-bonded electrons,has the potential to form three new chemical bonds.Herein,we explore a novel photocatalytic trifunctionalization of trifluoromethyl carbyne to synthesize 1-(het)aryl-2,2,2-trifluoroethyl 2-iodobenzoate,which is further converted intoα-(het)aryl trifluoromethylcarbinols of interest in medicinal chemistry through a hydrolysis process.To improve the practicality of this reaction and streamline the procedure,we achieve the assembly ofα-(het)aryl trifluoromethylcarbinols in a one-step reaction under mild conditions by adding LiPF and H_(2)O.A plausible catalytic pathway involves the direct C(sp^(2))-H bond diazotrifluoromethylation of(het)arenes with the diazotrifluoroethyl radical(N_(2)=C-CF_(3))generated from hypervalent iodine(III)reagent,followed by N_(2)extrusion and subsequent O-H bond insertion with H_(2)O to formα-(het)aryl(trifluoromethyl)carbenes.This efficient tandem process enables the one-pot,stepeconomical synthesis of α-aryl 2,2,2-trifluoroethanol derivatives,representing a unique approach for the straightforward synthesis of trifluoromethylcarbinols.展开更多
The widespread use of multifunctional metasurfaces has started to revolutionize conventional electromagnetic devices due to their unprecedented capabilities and exceedingly low losses.Specifically,geometric metasurfac...The widespread use of multifunctional metasurfaces has started to revolutionize conventional electromagnetic devices due to their unprecedented capabilities and exceedingly low losses.Specifically,geometric metasurfaces that utilize spatially varied single-celled elements to impart arbitrary phase modulation under circularly polarized(CP)waves have attracted more attention.However,the geometric phase has intrinsically opposite signs for two spins,resulting in locked and mirrored functionalities for the right-handed and left-handed CP beams.Additionally,the demonstrated geometric metasurfaces so far have been limited to operating in either transmission or reflection modes at a single wavelength.Here,we propose a double-layered metasurface composed of complementary elliptical and reversal ring resonator structures to achieve simultaneous and independent control of the reflection and transmission of CP waves at two independent terahertz frequencies,which integrates three functions of reflected beam deflection,reflected Bessel beam generation,and transmitted beam focusing on the whole space.The high efficiency and simple design of our metasurface will open new avenues for integrated terahertz metadevices with advanced functionalities.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22101237 and 22171233)Collaborative Fund of Luzhou Government and Southwest Medical University(Nos.2023LZXNYDJ019 and 2024LZXNYDJ050)+1 种基金the Science and Technology Program of Luzhou City(No.2024RCX207)the research fund of Southwest Medical University(Nos.2023QN091 and 2022QN057).
文摘N,O-Spiroaminals have potential biological activities and abilities to modulate the physicochemical and pharmacokinetic properties of drug molecules.However,effective catalytic methods for the efficient construction of N,O-spiroaminals are still limited to date.Herein,we report a novel 1,1,2-trifunctionalization of unactivated alkenes to rapidly and efficiently obtain a diverse array of architecturally intriguing N,O-spiroaminals.This methodology exhibits broad substrate scope,good functional group compatibility,and potential synthetic utility by a scale-up reaction,diverse product derivatizations and late-stage functionalization of complex biorelevant molecule.Notably,this transformation selectively allows for the formation of three new chemical bonds(C–O,C–C,and C–N)and one spiro quaternary carbon center across C-C double bonds.
基金supported by the National Natural Science Foundation of China(No.21925108)the Key Labora-of Xi'an(No.201805058ZD9CG42)。
文摘Main observation and conclusion Herein,we report a highly chemo-and regioselective vicinal trifunctionalization of aryl iodides by palladium/norbornene(Pd/NBE)catalysis.The key feature of this new method is the introduction of two distinct nitrogen and carbon electrophiles,with a large gap in reactivity,for ortho-unsubstituted aryl iodides via an intermolecular and intramolecular C―H functionalization,respectively.Eight types of ipso terminations can be coupled with both ortho-amination and ortho-alkylation,affording a variety of polysubstituted benzoheterocyclic scaffolds.Silicon-tethered substrates can lead to polyfucntional arenes via a single-step operation.Noteworthy,these products exhibit full-color-tunable strong fluorescence emissions with large Stokes shifts,and product 7r can serve as a fluorescent probe to specifically target lysosome in living cells.
文摘The first Cu-catalyzed 1,2,5-trifunctionalization of abundant terminal alkynes is realized by merging hydrogen atom transfer and traceless directing strategy with SR as a transient group,delivering highly functionalized aldehydes in moderate to excellent yields with broad substrate scope.The synthetic utility of this method was demonstrated by the gram-scale reaction and downstream transformations of the resultant products.Given the high efficient installation of three different functional groups in a single reaction,it can serve as a very attractive method for rapidly assembling complex molecules from readily available starting materials.
基金This work was supported by the Chinese Scholarship Council(CSC).
文摘Functionalized bisboryl compounds have recently emerged as a new class of synthetically useful building blocks in organic synthesis.Herein,we report an efficient strategy to synthesizeβ-geminal-diboryl ketones enabled by a Cu/Pd-catalyzed borocarbonylative trifunctionalization of readily available alkynes and allenes.This reaction promises to be a useful method for the synthesis of functionalizedβ-geminal-diboryl ketones with broad functional group tolerance.Mechanistic studies suggest that the reaction proceeds through borocarbonylation/hydroboration cascade of both alkynes and allenes.
基金supported by the National Natural Science Foundation of China(21971073,22001075,22231002)the Natural Science Foundation of Guangdong Province(2019A1515011468)+2 种基金the Discipline Construction Project of Guangdong Medical University(4SG23231G,4SG23249G)the Ordinary University Characteristic Innovation Project of Guangdong Province(2022KTSCX047)the Key-Area Research and Development Program of Guangdong Province(2020B010188001)。
文摘Carbon dioxide reduction, as a sustainable and versatile strategy for the access of chemical fuels, has attracted increasing attention and enormous efforts have been devoted to it in recent years. However, employing carbon dioxide as double synthons via bimolecular reduction remains challenging. Here, by leveraging the bimolecular reduction of carbon dioxide to carbonyl and methyl respectively, we describe a Pd-catalyzed trifunctionalization of alkynes with aryl iodide for the first time and showcase its advantages on the formation of various β-diketones and their application in the constructing of heterocyclic compounds with important biological activity, including pyrimidine, oxazole, pyrazole.
基金supported by the National Natural Science Foundation of China(21762054)the Guizhou Provincial Natural Science Foundation(QKHJC-2020-1Z072)+3 种基金the Outstanding Youth Talent Support Programs from Zunyi Medical University(18ZY-002)the Innovation and Entrepreneurship Training Program for College Students from Zunyi Medical University(ZYDC2019028)the Science and Technology Department of Zunyi(ZSKRPT-2020-5)the Fifth Batch of Talent Base in Guizhou Province(S-030-1)。
文摘Trifluoromethyl carbyne(CF_(3)?:),with its three non-bonded electrons,has the potential to form three new chemical bonds.Herein,we explore a novel photocatalytic trifunctionalization of trifluoromethyl carbyne to synthesize 1-(het)aryl-2,2,2-trifluoroethyl 2-iodobenzoate,which is further converted intoα-(het)aryl trifluoromethylcarbinols of interest in medicinal chemistry through a hydrolysis process.To improve the practicality of this reaction and streamline the procedure,we achieve the assembly ofα-(het)aryl trifluoromethylcarbinols in a one-step reaction under mild conditions by adding LiPF and H_(2)O.A plausible catalytic pathway involves the direct C(sp^(2))-H bond diazotrifluoromethylation of(het)arenes with the diazotrifluoroethyl radical(N_(2)=C-CF_(3))generated from hypervalent iodine(III)reagent,followed by N_(2)extrusion and subsequent O-H bond insertion with H_(2)O to formα-(het)aryl(trifluoromethyl)carbenes.This efficient tandem process enables the one-pot,stepeconomical synthesis of α-aryl 2,2,2-trifluoroethanol derivatives,representing a unique approach for the straightforward synthesis of trifluoromethylcarbinols.
基金supported by the Villum Fonden(No.37372)Independent Research Fund Denmark(No.1134-00010B)+1 种基金NaturalScienceFoundationofZhejiangProvince(No.LY19A040004)Natural Science Foundation of Ningbo(No.2021J073)。
文摘The widespread use of multifunctional metasurfaces has started to revolutionize conventional electromagnetic devices due to their unprecedented capabilities and exceedingly low losses.Specifically,geometric metasurfaces that utilize spatially varied single-celled elements to impart arbitrary phase modulation under circularly polarized(CP)waves have attracted more attention.However,the geometric phase has intrinsically opposite signs for two spins,resulting in locked and mirrored functionalities for the right-handed and left-handed CP beams.Additionally,the demonstrated geometric metasurfaces so far have been limited to operating in either transmission or reflection modes at a single wavelength.Here,we propose a double-layered metasurface composed of complementary elliptical and reversal ring resonator structures to achieve simultaneous and independent control of the reflection and transmission of CP waves at two independent terahertz frequencies,which integrates three functions of reflected beam deflection,reflected Bessel beam generation,and transmitted beam focusing on the whole space.The high efficiency and simple design of our metasurface will open new avenues for integrated terahertz metadevices with advanced functionalities.
