Comprehensive Summary Terpyridine ligands have been applied as a class of unique ligands due to their rich coordination chemistry in the catalysis.Herein,we developed a new class of C_(2)-symmetric chiral terpyridine-...Comprehensive Summary Terpyridine ligands have been applied as a class of unique ligands due to their rich coordination chemistry in the catalysis.Herein,we developed a new class of C_(2)-symmetric chiral terpyridine-pyrroloimidazolone ligands(TPy-BPI).Their catalytic activity was evaluated in the asymmetric Friedel-Crafts alkylation of indoles with 2,3-dioxopyrrolidines.Excellent yields(up to 92%)and high enantioselectivities(up to 97%ee)are obtained for a wide range of substrates under mild conditions.展开更多
Lignans have been established as a privileged scaffold in drug discovery,particularly in anticancer and antioxidant properties.Concise and efficient construction of lignans and their derivatives in a single operation ...Lignans have been established as a privileged scaffold in drug discovery,particularly in anticancer and antioxidant properties.Concise and efficient construction of lignans and their derivatives in a single operation holds great medicinal significance for structure-activity relationship studies yet remains challenging.Drawing inspiration from the biosynthesis of lignans,we present a general,high-step-economy palladium-catalyzed reaction that converts simple chemical feedstocks into dehydrodibenzylbutyrolactone lignans through the in-situ construction and coupling of two phenylpropanoid molecules.The diversity of organoboronic acids and the editability of enyne provide a powerful platform for the rapid construction of lignan libraries,featuring 82 lignans analogs,collective syntheses of 10 distinct lignan skeletons,and 13 hybrid molecules combining pharmacophore fragments with drug and derivatives.The subtle combination of phosphine ligands with quinones for switching chemoselectivity is vital to the success of this protocol.展开更多
Stereoselective synthesis of multi-substituted cyclobutanes with different substituents is still a daunting challenge in organic synthesis.We report here a practical and facile approach to synthesizing all-trans 2,3,4...Stereoselective synthesis of multi-substituted cyclobutanes with different substituents is still a daunting challenge in organic synthesis.We report here a practical and facile approach to synthesizing all-trans 2,3,4-trisubstituted cyclobutanones from readily available dichlorocyclobutanones.The substitution reaction proceeds smoothly via oxyallyl cation intermediates under mild basic conditions.Further transformation to the synthesis of 1,2,3,4-tetrasubstituted cyclobutanes was also explored.展开更多
Intermolecular hydrogen bonding among urea units grants prominent mechanical strength to polyurea elastomer materials.However,such interactions can cause significant solubility problems when synthesizing oligourea mac...Intermolecular hydrogen bonding among urea units grants prominent mechanical strength to polyurea elastomer materials.However,such interactions can cause significant solubility problems when synthesizing oligourea macrocycles with a large number of urea units,and it remains unknown for macrocycles containing more than six urea units.Here,we demonstrate a two-step,modular strategy for making a new class of tetraurea and octaurea macrocycles using commercially available building blocks.Intramolecular hydrogen bonding within the fundamental o-phenylene bis(urea)unit is the key to overcoming intermolecular hydrogen bonding to form favorable conformations for ring-closure reactions.The size and monomer sequences can be controlled by varying the flexibility of the spacers.Rigid diphenyl methylene and diphenyl ether linkers selectively afford tetraurea macrocycles,whereas the flexible hexylene linker produces octaurea macrocycles.Macrocycles encoded with two different spacers were also made.All these macrocycles are confirmed by X-ray diffraction structural analysis of the complexed forms with sulfate anions.Interestingly,a unique“figure-eight”structure is observed for the complex of MUH octaurea macrocycle with two encapsulated sulfate anions.Our study shows a paradigm of making large oligourea macrocycles with designer properties in a programable manner with tunable monomer sequences.展开更多
Transition-metal-catalyzed radical-mediated four-component carbonylation reactions offer a sustainable and efficient strategy for modular synthesis of complex carbonyl compounds from simple feedstocks.However,current ...Transition-metal-catalyzed radical-mediated four-component carbonylation reactions offer a sustainable and efficient strategy for modular synthesis of complex carbonyl compounds from simple feedstocks.However,current studies have primarily focused on the alkylcarbonylation ofπ-bonds in unsaturated hydrocarbons,including alkenes,alkynes and 1,3-enynes.In this study,we report a nickel-catalyzed 1,3-alkylcarbonylation ofσ-bonds in bicyclo[1.1.0]butanes(BCBs)using CO as an economical carbonyl source.展开更多
Chiral bipyridines represent a class of ligands noted for their distinctive reactivity and stereoselectivity in metal-catalyzed reactions.Herein,we have developed a new class of bifunctional C_(2)-symmetric chiral bip...Chiral bipyridines represent a class of ligands noted for their distinctive reactivity and stereoselectivity in metal-catalyzed reactions.Herein,we have developed a new class of bifunctional C_(2)-symmetric chiral bipyridine-type tetradentate ligands,abbreviated as Bpy-Bisulidines.These crab-shape ligands feature that:(1)bipyridine framework possesses the rich coordination ability with various metal ions;(2)chiral imidazolidine could generate a deep chiral pocket;(3)C_(2)-symmetry could reduce the number of possible transition states;(4)rigid chiral enviroments are close to the metal,and(5)imidazolidine N-H moiety acts as hydrogen-bonding donor.The newly developed chiral Bpy-Bisulidine ligands were successfully applied in Ni(II)-catalyzed asymmetric Friedel-Crafts alkylation reaction and inverse-electron-demand Hetero-Diels-Alder reactions,achieving excellent stereoselectivities.Our work is the first example of bifunctional C_(2)-symmetric chiral imidazolidine-type tetradentate ligands.X-ray crystallographic analysis of the Bpy-Bisulidine-Ni(OTf)_(2)complex,control experiments and linear correlation showed that the catalytically active species was a monomeric catalyst.展开更多
The first and asymmetric total syntheses of auriculatol D,micranthanoside IV,pierisformosides C,and I,glycosylated and highly unsaturated grayanoids,were achieved using a modular synthetic strategy.The glucosyls at C3...The first and asymmetric total syntheses of auriculatol D,micranthanoside IV,pierisformosides C,and I,glycosylated and highly unsaturated grayanoids,were achieved using a modular synthetic strategy.The glucosyls at C3-OH were selectively introduced via Wan glycosylation and Yu glycosylation,respectively.The tetracyclic architecture was assembled through a palladium-catalyzed coupling reaction and a lithiumhalogen exchange/intramolecular nucleophilic addition to the aldehyde sequence.The desaturation of the grayanoid core structure was achieved by the palladium-catalyzed elimination of an allylic ester.展开更多
A pentamodule assembly approach has been established for total synthesis of the naturally occurring(-)-palmyrolide A and(+)-5,7-epi-palmyrolide A.By using the racemic tert-butyl carbinol-containing alkyl iodide,the tw...A pentamodule assembly approach has been established for total synthesis of the naturally occurring(-)-palmyrolide A and(+)-5,7-epi-palmyrolide A.By using the racemic tert-butyl carbinol-containing alkyl iodide,the two diastereoisomeric macrolides could be obtained from the same sequence of reactions,demonstrating the flexibility of the multimodule assembly strategy for diverted total synthesis.展开更多
Taxanes are kinds of diterpenoids with important bioactivities,such as paclitaxel(taxol®)is an excellent natural broad-spectrum anticancer drug.Attempts to biosynthesize taxanes have made with limited success,mai...Taxanes are kinds of diterpenoids with important bioactivities,such as paclitaxel(taxol®)is an excellent natural broad-spectrum anticancer drug.Attempts to biosynthesize taxanes have made with limited success,mainly due to the bottleneck of the low efficiency catalytic elements.In this study,we developed an artificial synthetic system to produce taxanes from mevalonate(MVA)by coupling biological and chemical methods,which comprises in vitro multi-enzyme catalytic module,chemical catalytic module and yeast cell catalytic module.Through optimizing in vitro multienzyme catalytic system,the yield of taxadiene was increased to 946.7 mg/L from MVA within 8 h and the productivity was 14.2-fold higher than microbial fermentation.By incorporating palladium catalysis,the conversion rate of Taxa-4(20),11(12)-dien-5α-yl acetate(T5α-AC)reached 48%,effectively addressing the product promiscuity and the low yield rate of T5αOH.Finally,we optimized the expression of T10βOH in yeast resulting in the biosynthesis of Taxa-4(20),11(12)-dien-5α-acetoxy-10β-ol(T5α-AC-10β-ol)at a production of 15.8 mg/L,which displayed more than 2000-fold higher than that produced by co-culture fermentation strategy.These technologies offered a promising new approach for efficient synthesis of taxanes.展开更多
基金the financial support from the NSFC(22061006)Key Laboratory of Applied Surface and Colloid Chemistry(Shaanxi Normal University)of Ministry of Education,Natural Science Basic Research Plan in Shaanxi Province of China(No.2024JC-YBMS-119)+1 种基金Key Research and Development Plan Project of Xianyang(L2023-ZDYF-QYCX-030)Guizhou Provincial Basic Research Program(GCC[2023]078,ZK[2023]043,ZK[2022]144).
文摘Comprehensive Summary Terpyridine ligands have been applied as a class of unique ligands due to their rich coordination chemistry in the catalysis.Herein,we developed a new class of C_(2)-symmetric chiral terpyridine-pyrroloimidazolone ligands(TPy-BPI).Their catalytic activity was evaluated in the asymmetric Friedel-Crafts alkylation of indoles with 2,3-dioxopyrrolidines.Excellent yields(up to 92%)and high enantioselectivities(up to 97%ee)are obtained for a wide range of substrates under mild conditions.
基金Financial support was provided by the State Key Laboratory of Pulp and Paper Engineering(No.2022PY01)the National Natural Science Foundation of China(Nos.22231002 and 21871095)the Key-Area Research and Development Program of Guangdong Province(No.2020B010188001)。
文摘Lignans have been established as a privileged scaffold in drug discovery,particularly in anticancer and antioxidant properties.Concise and efficient construction of lignans and their derivatives in a single operation holds great medicinal significance for structure-activity relationship studies yet remains challenging.Drawing inspiration from the biosynthesis of lignans,we present a general,high-step-economy palladium-catalyzed reaction that converts simple chemical feedstocks into dehydrodibenzylbutyrolactone lignans through the in-situ construction and coupling of two phenylpropanoid molecules.The diversity of organoboronic acids and the editability of enyne provide a powerful platform for the rapid construction of lignan libraries,featuring 82 lignans analogs,collective syntheses of 10 distinct lignan skeletons,and 13 hybrid molecules combining pharmacophore fragments with drug and derivatives.The subtle combination of phosphine ligands with quinones for switching chemoselectivity is vital to the success of this protocol.
基金supported by the National Natural Science Foundation of China(22071028,21921003).
文摘Stereoselective synthesis of multi-substituted cyclobutanes with different substituents is still a daunting challenge in organic synthesis.We report here a practical and facile approach to synthesizing all-trans 2,3,4-trisubstituted cyclobutanones from readily available dichlorocyclobutanones.The substitution reaction proceeds smoothly via oxyallyl cation intermediates under mild basic conditions.Further transformation to the synthesis of 1,2,3,4-tetrasubstituted cyclobutanes was also explored.
基金supported by the National Natural Science Foundation of China(grant nos.21772154 and 91856102)the support of the Beijing Institute of Technology Research Fund Program for Young Scholars.
文摘Intermolecular hydrogen bonding among urea units grants prominent mechanical strength to polyurea elastomer materials.However,such interactions can cause significant solubility problems when synthesizing oligourea macrocycles with a large number of urea units,and it remains unknown for macrocycles containing more than six urea units.Here,we demonstrate a two-step,modular strategy for making a new class of tetraurea and octaurea macrocycles using commercially available building blocks.Intramolecular hydrogen bonding within the fundamental o-phenylene bis(urea)unit is the key to overcoming intermolecular hydrogen bonding to form favorable conformations for ring-closure reactions.The size and monomer sequences can be controlled by varying the flexibility of the spacers.Rigid diphenyl methylene and diphenyl ether linkers selectively afford tetraurea macrocycles,whereas the flexible hexylene linker produces octaurea macrocycles.Macrocycles encoded with two different spacers were also made.All these macrocycles are confirmed by X-ray diffraction structural analysis of the complexed forms with sulfate anions.Interestingly,a unique“figure-eight”structure is observed for the complex of MUH octaurea macrocycle with two encapsulated sulfate anions.Our study shows a paradigm of making large oligourea macrocycles with designer properties in a programable manner with tunable monomer sequences.
基金support from the National Natural Science Foundation of China(No.22171220)the XJTU Research Fund for Al Science is greatly appreciated.
文摘Transition-metal-catalyzed radical-mediated four-component carbonylation reactions offer a sustainable and efficient strategy for modular synthesis of complex carbonyl compounds from simple feedstocks.However,current studies have primarily focused on the alkylcarbonylation ofπ-bonds in unsaturated hydrocarbons,including alkenes,alkynes and 1,3-enynes.In this study,we report a nickel-catalyzed 1,3-alkylcarbonylation ofσ-bonds in bicyclo[1.1.0]butanes(BCBs)using CO as an economical carbonyl source.
基金the financial support from the NSFC(22361009)Guizhou Provincial Basic Research Program(GCC[2023]078,ZK[2023]043,ZK[2024]374).
文摘Chiral bipyridines represent a class of ligands noted for their distinctive reactivity and stereoselectivity in metal-catalyzed reactions.Herein,we have developed a new class of bifunctional C_(2)-symmetric chiral bipyridine-type tetradentate ligands,abbreviated as Bpy-Bisulidines.These crab-shape ligands feature that:(1)bipyridine framework possesses the rich coordination ability with various metal ions;(2)chiral imidazolidine could generate a deep chiral pocket;(3)C_(2)-symmetry could reduce the number of possible transition states;(4)rigid chiral enviroments are close to the metal,and(5)imidazolidine N-H moiety acts as hydrogen-bonding donor.The newly developed chiral Bpy-Bisulidine ligands were successfully applied in Ni(II)-catalyzed asymmetric Friedel-Crafts alkylation reaction and inverse-electron-demand Hetero-Diels-Alder reactions,achieving excellent stereoselectivities.Our work is the first example of bifunctional C_(2)-symmetric chiral imidazolidine-type tetradentate ligands.X-ray crystallographic analysis of the Bpy-Bisulidine-Ni(OTf)_(2)complex,control experiments and linear correlation showed that the catalytically active species was a monomeric catalyst.
基金the Science and Technology Major Program of Gansu Province of China(grant nos.22ZD6FA006,23ZDFA015,and 24ZD13FA017)the National Natural Science Foundation of China(grant nos.22322105 and 22071089)the Fundamental Research Funds for the Central Universities(grant no.lzujbky-2023-ey01).
文摘The first and asymmetric total syntheses of auriculatol D,micranthanoside IV,pierisformosides C,and I,glycosylated and highly unsaturated grayanoids,were achieved using a modular synthetic strategy.The glucosyls at C3-OH were selectively introduced via Wan glycosylation and Yu glycosylation,respectively.The tetracyclic architecture was assembled through a palladium-catalyzed coupling reaction and a lithiumhalogen exchange/intramolecular nucleophilic addition to the aldehyde sequence.The desaturation of the grayanoid core structure was achieved by the palladium-catalyzed elimination of an allylic ester.
基金This work is supported in part by a General Research Fund grant(601211)from the Research Grant CouncilThe Hong Kong Special Administrative Region,P.R.China+1 种基金The Hong Kong Chiu Chow Chamber of Commence HKUST Scholarship for Ph.D.Study(Y.L.)the Department of Chemistry,HKUST.
文摘A pentamodule assembly approach has been established for total synthesis of the naturally occurring(-)-palmyrolide A and(+)-5,7-epi-palmyrolide A.By using the racemic tert-butyl carbinol-containing alkyl iodide,the two diastereoisomeric macrolides could be obtained from the same sequence of reactions,demonstrating the flexibility of the multimodule assembly strategy for diverted total synthesis.
基金supported in part by the National Natural Science Foundation of China(32371499,31901026 and 32172443),China Postdoctoral Science Foundation(2019M661032)National Key R&D Program of China(2020YFA0908000 and 2022YFD1700400)+1 种基金the Frontiers Science Center for New Organic Matter,Nankai University(63181206)he Tianjin Development Program for Innovation and Entrepreneurship(2019-06).
文摘Taxanes are kinds of diterpenoids with important bioactivities,such as paclitaxel(taxol®)is an excellent natural broad-spectrum anticancer drug.Attempts to biosynthesize taxanes have made with limited success,mainly due to the bottleneck of the low efficiency catalytic elements.In this study,we developed an artificial synthetic system to produce taxanes from mevalonate(MVA)by coupling biological and chemical methods,which comprises in vitro multi-enzyme catalytic module,chemical catalytic module and yeast cell catalytic module.Through optimizing in vitro multienzyme catalytic system,the yield of taxadiene was increased to 946.7 mg/L from MVA within 8 h and the productivity was 14.2-fold higher than microbial fermentation.By incorporating palladium catalysis,the conversion rate of Taxa-4(20),11(12)-dien-5α-yl acetate(T5α-AC)reached 48%,effectively addressing the product promiscuity and the low yield rate of T5αOH.Finally,we optimized the expression of T10βOH in yeast resulting in the biosynthesis of Taxa-4(20),11(12)-dien-5α-acetoxy-10β-ol(T5α-AC-10β-ol)at a production of 15.8 mg/L,which displayed more than 2000-fold higher than that produced by co-culture fermentation strategy.These technologies offered a promising new approach for efficient synthesis of taxanes.
