Treponema is a Gram-negative anaerobic bacterium,among which the pathogenic Treponema can cause various diseases,such as venereal syphilis(Treponema pallidum),yaws(Treponema carateum),and oral diseases(Treponema denti...Treponema is a Gram-negative anaerobic bacterium,among which the pathogenic Treponema can cause various diseases,such as venereal syphilis(Treponema pallidum),yaws(Treponema carateum),and oral diseases(Treponema denticola and Treponema medium).Although different from conventional lipopolysaccharides,the extracellular glycoconjugate of Treponema may still be a potential antigen and provide a candidate for vaccine development.Hence,we completed the first chemical synthesis of Treponema medium ATCC 700293 tetrasaccharide precursor containing L-ornithine(L-Orn)and D-aspartic acid(D-Asp)derivatives.The efficiency of non-reducing end disaccharide formation has been improved by optimizing the assembly of the protecting groups in the donors and acceptors.Our[3+1]glycosylation strategy attempted to reduce the length of the acceptor to increase the nucleophilicity of the hydroxyl group,thereby improving the efficiency of synthesizing the target tetrasaccharide.The L-Orn derivative was introduced at the final stage due to its influence on the glycosylation stereospecificity and efficiency.Therefore,the successful introduction of two amino acid derivatives and the synthesis of a tetrasaccharide precursor with complex functional-group modifications have provided valuable insights for synthesizing other complex bacterial glycans.展开更多
Imine bonds are among the most explored building motifs in dynamic chemistry,polymers,and materials,and yet,their acid-resistance remains a longstanding issue.Herein we demonstrate a concept of internal protecting gro...Imine bonds are among the most explored building motifs in dynamic chemistry,polymers,and materials,and yet,their acid-resistance remains a longstanding issue.Herein we demonstrate a concept of internal protecting groups for improving the kinetic stability of dynamic imine bonds and polymers.Systematic examination of structure-reactivity relationship of a series of aldehydes/imines bearing a neighboring carboxyl allowed uncovering of required structural features for dynamically masking imine bonds with cyclic structures.Mechanistic studies indicated that noncovalent interactions along with sterics control the ringchain equilibrium and the stability of imine bonds.The incorporation of internal protecting groups into imine polymers further enabled their controlled stability in acidic media.Moreover,a combination of dynamic covalent network and coordination supramolecular network provided a facile means for the modulation of luminescent and mechanical properties of polymers.The strategies and results reported should be beneficial to molecular assemblies,dynamic polymers,biological delivery,and intelligent materials.展开更多
Goodyeroside A 1,a natural product with hepatoprotective activity,was efficiently synthesized in a total yield of 47% in five steps starting from (S)-malic acid. The spectral data of the target compound 1 is identical...Goodyeroside A 1,a natural product with hepatoprotective activity,was efficiently synthesized in a total yield of 47% in five steps starting from (S)-malic acid. The spectral data of the target compound 1 is identical with those of the natural product.展开更多
Various alcohols and phenols were trimethylsilylated in excellent yields using hexamethyldisilazane in the presence of catalytic amounts of environmentally friendly, hydrophobic, highly thermal stable, and completely ...Various alcohols and phenols were trimethylsilylated in excellent yields using hexamethyldisilazane in the presence of catalytic amounts of environmentally friendly, hydrophobic, highly thermal stable, and completely heterogeneous sulfonic acid functionalized mesostructured SBA-15 in dichloromethane at ambient temperature. Primary, bulky secondary, tertiary, and phenolic hydroxyl functional groups were transformed to the corresponding trimethylsilyl ethers in excellent yields. The simple experimental procedure was accompanied by easy recovery and the catalyst was reusable (at least 18 reaction cycles); these are attractive features of this protocol.展开更多
A new IL-supported diol, 1-（2,3-dihydroxypropyl）-3-methylimidazolium hexafluorophosphate has been synthesized and characterized by Fr-IR, ^1H NMR, ^13C NMR and MS （ESI）. Its physical properties such as freezing po...A new IL-supported diol, 1-（2,3-dihydroxypropyl）-3-methylimidazolium hexafluorophosphate has been synthesized and characterized by Fr-IR, ^1H NMR, ^13C NMR and MS （ESI）. Its physical properties such as freezing point, solubility and specific gravity and thermal stability were determined. Synthetic utilities of the resultant diol as a protecting group for aldehydes were also investigated.展开更多
Cedrane sesquiterpenes possess common tricyclo[5.3.1.0^(1,5)]undecane core structure.The varied oxa-five-membered ring decorating their core structure to form 8-oxa-tetracyclo[7.2.2.0^(1,5).0^(6,13)]tridecane framewor...Cedrane sesquiterpenes possess common tricyclo[5.3.1.0^(1,5)]undecane core structure.The varied oxa-five-membered ring decorating their core structure to form 8-oxa-tetracyclo[7.2.2.0^(1,5).0^(6,13)]tridecane framework,containing six consecutive chiral centers(including two all-carbon quaternary centers and one oxygenated quaternary carbon center),has proven to be a synthetic challenge and a biosynthetic mystery to date.展开更多
The evolution of synthetic design toward the efficient synthesis of cyclobutane natural product(±)-piperarborenine B is demonstrated.Taking the advantages of good functional group compatibility of contractive syn...The evolution of synthetic design toward the efficient synthesis of cyclobutane natural product(±)-piperarborenine B is demonstrated.Taking the advantages of good functional group compatibility of contractive synthesis of cyclobutanes from pyrrolidines,stereoselective synthesis of unsymmetric highly functionalized cyclobutanes core of(±)-piperarborenine B was realized in one step.Also,an unprecedented carboxylic acid assisted-diastereoselective Kracho decarboxylation/transmethylation features a new strategy for a non-symmetrical cyclobutane core.The synthesis of(±)-piperarborenine B illustrates the advancement of methodology resulting in the improvement in synthetic efficiency.展开更多
基金the National Natural Science Foundation of China(22325803,22077052,22277042,22107037,22177041,22207042)the China Postdoctoral Science Foundation(2021M691279)the National Key R&D Program of China(2023YFC2308000).
文摘Treponema is a Gram-negative anaerobic bacterium,among which the pathogenic Treponema can cause various diseases,such as venereal syphilis(Treponema pallidum),yaws(Treponema carateum),and oral diseases(Treponema denticola and Treponema medium).Although different from conventional lipopolysaccharides,the extracellular glycoconjugate of Treponema may still be a potential antigen and provide a candidate for vaccine development.Hence,we completed the first chemical synthesis of Treponema medium ATCC 700293 tetrasaccharide precursor containing L-ornithine(L-Orn)and D-aspartic acid(D-Asp)derivatives.The efficiency of non-reducing end disaccharide formation has been improved by optimizing the assembly of the protecting groups in the donors and acceptors.Our[3+1]glycosylation strategy attempted to reduce the length of the acceptor to increase the nucleophilicity of the hydroxyl group,thereby improving the efficiency of synthesizing the target tetrasaccharide.The L-Orn derivative was introduced at the final stage due to its influence on the glycosylation stereospecificity and efficiency.Therefore,the successful introduction of two amino acid derivatives and the synthesis of a tetrasaccharide precursor with complex functional-group modifications have provided valuable insights for synthesizing other complex bacterial glycans.
基金the National Natural Science Foundation of China(NSFC,Nos.22071247,92156010,22101283,and 22101284)the Key Research Program of Frontier Sciences(No.QYZDBSSW-SLH030)of the CAS+1 种基金Natural Science Foundation of Fujian Province(Nos.2020J06035 and 2022J05085)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR112)for support.
文摘Imine bonds are among the most explored building motifs in dynamic chemistry,polymers,and materials,and yet,their acid-resistance remains a longstanding issue.Herein we demonstrate a concept of internal protecting groups for improving the kinetic stability of dynamic imine bonds and polymers.Systematic examination of structure-reactivity relationship of a series of aldehydes/imines bearing a neighboring carboxyl allowed uncovering of required structural features for dynamically masking imine bonds with cyclic structures.Mechanistic studies indicated that noncovalent interactions along with sterics control the ringchain equilibrium and the stability of imine bonds.The incorporation of internal protecting groups into imine polymers further enabled their controlled stability in acidic media.Moreover,a combination of dynamic covalent network and coordination supramolecular network provided a facile means for the modulation of luminescent and mechanical properties of polymers.The strategies and results reported should be beneficial to molecular assemblies,dynamic polymers,biological delivery,and intelligent materials.
文摘Goodyeroside A 1,a natural product with hepatoprotective activity,was efficiently synthesized in a total yield of 47% in five steps starting from (S)-malic acid. The spectral data of the target compound 1 is identical with those of the natural product.
文摘Various alcohols and phenols were trimethylsilylated in excellent yields using hexamethyldisilazane in the presence of catalytic amounts of environmentally friendly, hydrophobic, highly thermal stable, and completely heterogeneous sulfonic acid functionalized mesostructured SBA-15 in dichloromethane at ambient temperature. Primary, bulky secondary, tertiary, and phenolic hydroxyl functional groups were transformed to the corresponding trimethylsilyl ethers in excellent yields. The simple experimental procedure was accompanied by easy recovery and the catalyst was reusable (at least 18 reaction cycles); these are attractive features of this protocol.
基金the National Natural Science Foundation of China(No.20533010,20673039)the Science&Technology Commission of Shanghai Municipality(No.06JC14023)for financial support.
文摘A new IL-supported diol, 1-（2,3-dihydroxypropyl）-3-methylimidazolium hexafluorophosphate has been synthesized and characterized by Fr-IR, ^1H NMR, ^13C NMR and MS （ESI）. Its physical properties such as freezing point, solubility and specific gravity and thermal stability were determined. Synthetic utilities of the resultant diol as a protecting group for aldehydes were also investigated.
基金Financial support from the National Natural Science Founda-tion of China(Nos.21971096,21772079,&21672088)the Natural Science Foundation of Gansu Province(No.18JR4RA003)is acknowledged.
文摘Cedrane sesquiterpenes possess common tricyclo[5.3.1.0^(1,5)]undecane core structure.The varied oxa-five-membered ring decorating their core structure to form 8-oxa-tetracyclo[7.2.2.0^(1,5).0^(6,13)]tridecane framework,containing six consecutive chiral centers(including two all-carbon quaternary centers and one oxygenated quaternary carbon center),has proven to be a synthetic challenge and a biosynthetic mystery to date.
基金A.P.A.thanks for the support of the DFG(No.AN 1064/4–1)and the Boehringer Ingelheim Foundation(Plus 3).C.H.thanks the International Max Planck Research School for Living Matter(Dortmund,Germany).
文摘The evolution of synthetic design toward the efficient synthesis of cyclobutane natural product(±)-piperarborenine B is demonstrated.Taking the advantages of good functional group compatibility of contractive synthesis of cyclobutanes from pyrrolidines,stereoselective synthesis of unsymmetric highly functionalized cyclobutanes core of(±)-piperarborenine B was realized in one step.Also,an unprecedented carboxylic acid assisted-diastereoselective Kracho decarboxylation/transmethylation features a new strategy for a non-symmetrical cyclobutane core.The synthesis of(±)-piperarborenine B illustrates the advancement of methodology resulting in the improvement in synthetic efficiency.
