Biomineralization process regulates the growth of inorganic minerals by complex molecules,proteins,and cells,endowing bio-materials with marvels structures and excellent properties.The intricate structures and composi...Biomineralization process regulates the growth of inorganic minerals by complex molecules,proteins,and cells,endowing bio-materials with marvels structures and excellent properties.The intricate structures and compositions found in biominerals have inspired scientists to design and synthesize numerous artificial biomimetic materials.The methodology for controlling the formation of inorganics plays a pivotal role in achieving biomimetic structures and compositions.However,the current approach predominantly relies on the classical nucleation theory,which hinders the precise preparation of inorganic materials by replicating the biomineralization strategy.Recently,the development of“inorganic ionic polymerization”strategy has enabled us to regulate the arrangement of inorganic ions from solution to solid phase,which establishes an artificial way to produce inorganic materials analogous to the biomineralization process.Based on inorganic ionic polymerization,a series of achievements have been realized for the biomimetic preparation,including moldable construction of inorganic materials,hard tissue regeneration,and high-performance biomimetic materials.Moreover,the utilization of inorganic ionic polymerization has also facilitated the production of numerous advanced materials,including novel structures that exceed the current knowledge of materials science.The inorganic ionic polymerization system provides new artificial strategies and methodologies for the controllable synthesis of inorganics,which mimics the biomineralization process,paving the way for the future development of more high-performance materials.展开更多
A new synthetic approach to elvucitabine started from L-xylose via the reactions of 10 steps in an overall yield of 20% was developed. The key steps included trimethylsilyl trifluoromethanesulfonate(TMSOT0-mediated s...A new synthetic approach to elvucitabine started from L-xylose via the reactions of 10 steps in an overall yield of 20% was developed. The key steps included trimethylsilyl trifluoromethanesulfonate(TMSOT0-mediated stereocontrolled β-glycosidation and exquisite choice of chloroacetyl group for the protection of hydroxyl groups as well as the corresponding deprotection under notably mild conditions. The structure of elvucitabine, in particular, the stereochemistry thereof, was unambiguously determined by comparison of the physical properties, such as 1H NMR data and the specific rotation, of the synthesized sample with those reported.展开更多
Directing group-assisted, transition metal-catalyzed three-component difunctionalization of alkenes has emerged as a powerful tool to drive molecular complexity. However, this strategy generally works with the substra...Directing group-assisted, transition metal-catalyzed three-component difunctionalization of alkenes has emerged as a powerful tool to drive molecular complexity. However, this strategy generally works with the substrates bearing directing groups in close proximity to the alkene moieties, due to the preference for formation of kinetically stable five-membered metallacycles. Herein, we have disclosed a complementary strategy to accomplish a nickel-catalyzed remote arylalkylation of alkenyl amines with excellent regioselectivity and diastereofidelity, involving rare six- or seven-membered metallacycles. This general protocol is compatible with a series of δ- and ε-alkenyl amines, providing corresponding valuable δ,ε- and ε,ζ-difunctionalized aliphatic amines that would be difficult to synthesize. The coordination of the bidentate picolinamide auxiliary and the facile oxidative addition of alkyl halides to Ni(I) species are the key to the success of the developed remote olefin dicarbofunctionalization.展开更多
A simple protocol for the sulfur-promoted conversion of aromatic aldehydes to aromatic nitriles has been developed.This strategy enables the one-pot conversion of inexpensive and readily available aromatic aldehydes i...A simple protocol for the sulfur-promoted conversion of aromatic aldehydes to aromatic nitriles has been developed.This strategy enables the one-pot conversion of inexpensive and readily available aromatic aldehydes into highly valuable aromatic nitriles using a cheap inorganic ammonium salt as the nitrogen source in the absence of metals.Significantly,a broad scope of substrates was explored using this strategy,and various groups,including alkyl,alkoxyl,alkylthiol,hydroxyl,amino,aryl,alkenyl,cyano,carboxyl,and borate ester groups were tolerated,and good to excellent yields were achieved in most cases.Additionally,polycyclic aromatic aldehydes and heteroaromatic aldehydes also could be converted to the corre-sponding nitriles with satisfactory yields.This method can be utilized as a powerful tool for the cyanation of complex molecules.展开更多
Many cyclobutane natural products have intriguing biological properties that arise from their fascinating chemical structures.Cyclobutane natural products feature a cyclobutane scaffold as the core or as a part of the...Many cyclobutane natural products have intriguing biological properties that arise from their fascinating chemical structures.Cyclobutane natural products feature a cyclobutane scaffold as the core or as a part of the spirocyclic or fused cyclic core.However,the highly functionalized nature and the inherent stereochemistry of these cyclobutane natural products,which are associated with their biological activities,pose tremendous challenges to their preparation.In this perspective,we present contemporary advancements in synthetic methods and/or strategies en route to the bioactive cyclobutane natural products.We begin by describing the representative bioactive cyclobutane natural products and then focus on illustrative examples of their syntheses reported from 2018 to 2021.These advances will enable efficient syntheses of cyclobutanes of structural and biological importance.展开更多
A strategy for the synthesis of benzisothiazoles by a three-component reaction was developed using elemental sulfur and ammonium as heteroatom components under transition metal-free conditions.The reaction is preferab...A strategy for the synthesis of benzisothiazoles by a three-component reaction was developed using elemental sulfur and ammonium as heteroatom components under transition metal-free conditions.The reaction is preferably based on pyridine or quinoline ring substrate,and good to excellent yields can be obtained.Notably,this reaction has been applied to the gram-scale synthesis of bioactive molecules.展开更多
基金supports from the National Natural Science Foundation of China(Nos.22022511 and 22275161)the National Key Research and Development Program of China(No.2020YFA0710400)the Fundamental Research Funds for the Central Universities(Nos.2021FZZX001-04 and 2022ZJJH02-01).
文摘Biomineralization process regulates the growth of inorganic minerals by complex molecules,proteins,and cells,endowing bio-materials with marvels structures and excellent properties.The intricate structures and compositions found in biominerals have inspired scientists to design and synthesize numerous artificial biomimetic materials.The methodology for controlling the formation of inorganics plays a pivotal role in achieving biomimetic structures and compositions.However,the current approach predominantly relies on the classical nucleation theory,which hinders the precise preparation of inorganic materials by replicating the biomineralization strategy.Recently,the development of“inorganic ionic polymerization”strategy has enabled us to regulate the arrangement of inorganic ions from solution to solid phase,which establishes an artificial way to produce inorganic materials analogous to the biomineralization process.Based on inorganic ionic polymerization,a series of achievements have been realized for the biomimetic preparation,including moldable construction of inorganic materials,hard tissue regeneration,and high-performance biomimetic materials.Moreover,the utilization of inorganic ionic polymerization has also facilitated the production of numerous advanced materials,including novel structures that exceed the current knowledge of materials science.The inorganic ionic polymerization system provides new artificial strategies and methodologies for the controllable synthesis of inorganics,which mimics the biomineralization process,paving the way for the future development of more high-performance materials.
文摘A new synthetic approach to elvucitabine started from L-xylose via the reactions of 10 steps in an overall yield of 20% was developed. The key steps included trimethylsilyl trifluoromethanesulfonate(TMSOT0-mediated stereocontrolled β-glycosidation and exquisite choice of chloroacetyl group for the protection of hydroxyl groups as well as the corresponding deprotection under notably mild conditions. The structure of elvucitabine, in particular, the stereochemistry thereof, was unambiguously determined by comparison of the physical properties, such as 1H NMR data and the specific rotation, of the synthesized sample with those reported.
基金This work was supported by the National Natural Science Foundation of China(21901185,22002037)the Innovation and Entrepreneurship Training Programme for University Students(202110546007)+1 种基金the Scientific Research Hunan Provincial Education Department(19A068)funds provided by Tianjin Normal University.
文摘Directing group-assisted, transition metal-catalyzed three-component difunctionalization of alkenes has emerged as a powerful tool to drive molecular complexity. However, this strategy generally works with the substrates bearing directing groups in close proximity to the alkene moieties, due to the preference for formation of kinetically stable five-membered metallacycles. Herein, we have disclosed a complementary strategy to accomplish a nickel-catalyzed remote arylalkylation of alkenyl amines with excellent regioselectivity and diastereofidelity, involving rare six- or seven-membered metallacycles. This general protocol is compatible with a series of δ- and ε-alkenyl amines, providing corresponding valuable δ,ε- and ε,ζ-difunctionalized aliphatic amines that would be difficult to synthesize. The coordination of the bidentate picolinamide auxiliary and the facile oxidative addition of alkyl halides to Ni(I) species are the key to the success of the developed remote olefin dicarbofunctionalization.
基金This work was supported by the Key Project Program of the Educational Department of Hunan Province(No.18A069)the Postgraduate Scientific Research Innovation Project of Hunan Province(No.QL20210148)+3 种基金the Scientific Research Foundation of Hunan Provincial Education Department(No.19C0522)the Scientific Research Foundation of Hunan Institute of Technology(No.2018HY011)the Project of Innovation Team of the Ministry of Education(No.IRT_17R90)Hunan 2011 Collaborative Innovation Center of Chemical Engineering&Technology with Environmental Benignity and Effective Resource Utilization.
文摘A simple protocol for the sulfur-promoted conversion of aromatic aldehydes to aromatic nitriles has been developed.This strategy enables the one-pot conversion of inexpensive and readily available aromatic aldehydes into highly valuable aromatic nitriles using a cheap inorganic ammonium salt as the nitrogen source in the absence of metals.Significantly,a broad scope of substrates was explored using this strategy,and various groups,including alkyl,alkoxyl,alkylthiol,hydroxyl,amino,aryl,alkenyl,cyano,carboxyl,and borate ester groups were tolerated,and good to excellent yields were achieved in most cases.Additionally,polycyclic aromatic aldehydes and heteroaromatic aldehydes also could be converted to the corre-sponding nitriles with satisfactory yields.This method can be utilized as a powerful tool for the cyanation of complex molecules.
基金J.Liu acknowledges the support of the Guangdong Basic and Applied Basic Research Foundation(No.2021A1515010188)the Shenzhen Science and Technology Innovation Committee(No.JCYJ20190809181011411)+1 种基金the Guangdong Department of Education(No.2021ZDJS097)Y.Xie gratefully acknowledges the financial support from the National Natural Science Foundation of China(No.22107058).
文摘Many cyclobutane natural products have intriguing biological properties that arise from their fascinating chemical structures.Cyclobutane natural products feature a cyclobutane scaffold as the core or as a part of the spirocyclic or fused cyclic core.However,the highly functionalized nature and the inherent stereochemistry of these cyclobutane natural products,which are associated with their biological activities,pose tremendous challenges to their preparation.In this perspective,we present contemporary advancements in synthetic methods and/or strategies en route to the bioactive cyclobutane natural products.We begin by describing the representative bioactive cyclobutane natural products and then focus on illustrative examples of their syntheses reported from 2018 to 2021.These advances will enable efficient syntheses of cyclobutanes of structural and biological importance.
基金This work was supported by the Key Project Program of the Educational Department of Hunan Province(No.18A069)the Postgraduate Scientific Research Innovation Project of Hunan Province(No.QL20210148)+3 种基金the Scientific Research Foundation of Hunan Provincial Education Department(No.19C0522)the Scientific Research Foundation of Hunan Institute of Technology(No.2018HY011)the Project of Innovation Team of the Ministry of Education(No.IRT_17R90)Hunan 2011 Collaborative Innovation Center of Chemical Engineering&Technology with Environmental Benignity and Effective Resource Utilization.
文摘A strategy for the synthesis of benzisothiazoles by a three-component reaction was developed using elemental sulfur and ammonium as heteroatom components under transition metal-free conditions.The reaction is preferably based on pyridine or quinoline ring substrate,and good to excellent yields can be obtained.Notably,this reaction has been applied to the gram-scale synthesis of bioactive molecules.