A Lewis base catalyzed ring expansion of isatin with 2,2,2-trifluorodiazoethane(CF3 CHN2)is developed.It is characterized that the merge of tetramethylethylenediamine and CF3 CHN2 generates reactive triazene intermedi...A Lewis base catalyzed ring expansion of isatin with 2,2,2-trifluorodiazoethane(CF3 CHN2)is developed.It is characterized that the merge of tetramethylethylenediamine and CF3 CHN2 generates reactive triazene intermediates,which construct substituted 3-hydroxy-4-(trifluoromethyl)quinolinones with high efficiency.Synthetic application of the procedure is broadened by 3-trifluormethylpyrazole fused3-hydroxy-4-(trifluoromethyl)quinolinone synthesis.展开更多
A photoinduced copper-catalyzed alkoxyl triggered C-C bond cleavage/aminocarbonylation cascade is presented.Through adjusting the structure of alkoxyl radical precursors,functionalized lactones and ketoamides were syn...A photoinduced copper-catalyzed alkoxyl triggered C-C bond cleavage/aminocarbonylation cascade is presented.Through adjusting the structure of alkoxyl radical precursors,functionalized lactones and ketoamides were synthesized with good yields and excellent functional group tolerance under redox-neutral conditions.Notably,this protocol enables the integration of lactone fragments with many amine drugs and drug fragments.展开更多
Six-membered and seven-membered carbocycles are prevalent in nature due to their low ring strain and structural stability.In this work,we introduce a novel photocatalytic skeletal editing strategy for Dowd-Beckwith ri...Six-membered and seven-membered carbocycles are prevalent in nature due to their low ring strain and structural stability.In this work,we introduce a novel photocatalytic skeletal editing strategy for Dowd-Beckwith ring expansion acylation,leveraging tetrabutylammonium decatungstate(TBADT)as a hydrogen atom transfer(HAT)photocatalyst.This innovative approach enables the efficient synthesis of a diverse range of six-and seven-membered cyclic ketones under mild conditions,offering key advantages including environmental sustainability,high atom and step economy,good functional group tolerance,and the potential for extensive downstream functionalization.The versatility of this strategy is further demonstrated by its successful application in the post-synthetic modification of complex pharmaceutical intermediates and its scalability via continuous-flow technology,underscoring its broad utility in synthetic chemistry and pharmaceutical development.展开更多
Polymer chain architectures play a crucial role in the physical properties of polymers and this unique phenomenon has been recognized as the topological effects.As one of the most representative architectures,macrocyc...Polymer chain architectures play a crucial role in the physical properties of polymers and this unique phenomenon has been recognized as the topological effects.As one of the most representative architectures,macrocyclic polymers characterized by the endless topology have received extensive attention due to their distinct physical properties as compared to the linear counterparts.To understand these differences and unravel the underlying mechanisms,there is a long pursuit to efficiently fabricate macrocyclic polymers.To date,both ring-closing and ring-expansion strategies have been developed,which drastically elevates the accessibility of macrocyclic polymers.The improved availability of macrocyclic polymers enables the further investigation of the biomedical applications and the preliminary results suggest that macrocyclic polymers outperform their linear analogs in terms of improving gene delivery efficiency,elevating blood circulation time,and enhancing colloidal stability of nanoparticles.展开更多
The Pictet-Spengler/transamination cascade reaction enables modular synthesis of marinoquinoline analoviphrough three-component indole ring-expansion/cyclization in the manner of novel N1–C2 cleavage of indoles.Thi...The Pictet-Spengler/transamination cascade reaction enables modular synthesis of marinoquinoline analoviphrough three-component indole ring-expansion/cyclization in the manner of novel N1–C2 cleavage of indoles.This metal-free protocol exhibits very broad functional group tolerance with up to quantitative yields. Preliminarystudies on the antitumor activity of the resultant marinoquinoline analogues reveal that the indolyl-attachedpyrrolo[2,3-c]quinoline product (5d) shows great potential (IC50 of 0.32 μg/mL to HeLa cells) as a promisinganticancer agent in clinic.展开更多
基金financial support from the National Natural Science Foundation of China(No.81602977)the CAMS Innovation Fund for Medical Sciences(Nos.2019-RC-HL-010,2017-I2M-1013)+1 种基金the Science and Technology Development Project of Jilin Province of China(No.20190304050YY)China Association of Chinese Medicine(No.2017QNRC001)。
文摘A Lewis base catalyzed ring expansion of isatin with 2,2,2-trifluorodiazoethane(CF3 CHN2)is developed.It is characterized that the merge of tetramethylethylenediamine and CF3 CHN2 generates reactive triazene intermediates,which construct substituted 3-hydroxy-4-(trifluoromethyl)quinolinones with high efficiency.Synthetic application of the procedure is broadened by 3-trifluormethylpyrazole fused3-hydroxy-4-(trifluoromethyl)quinolinone synthesis.
基金Financial support from the National Natural Science Foundation of China(Nos.21971201,22171220)the Fundamental Research Funds of the Central Universities(No.xtr072022003)。
文摘A photoinduced copper-catalyzed alkoxyl triggered C-C bond cleavage/aminocarbonylation cascade is presented.Through adjusting the structure of alkoxyl radical precursors,functionalized lactones and ketoamides were synthesized with good yields and excellent functional group tolerance under redox-neutral conditions.Notably,this protocol enables the integration of lactone fragments with many amine drugs and drug fragments.
基金supported by the National Natural Science Foundation of China(22071222,22171249)the 111 Project(D20003)+3 种基金the Science&Technology Innovation Talents in Universities of Henan Province(23HASTIT003)the Natural Science Foundation of Henan Province(242301420006,252300421245)the High-level Talent Research Start-up Project Funding of Henan Academy of Sciences(20251818003)the Zhongyuan Leading Young Talents in Scientific and Technological Innovation。
文摘Six-membered and seven-membered carbocycles are prevalent in nature due to their low ring strain and structural stability.In this work,we introduce a novel photocatalytic skeletal editing strategy for Dowd-Beckwith ring expansion acylation,leveraging tetrabutylammonium decatungstate(TBADT)as a hydrogen atom transfer(HAT)photocatalyst.This innovative approach enables the efficient synthesis of a diverse range of six-and seven-membered cyclic ketones under mild conditions,offering key advantages including environmental sustainability,high atom and step economy,good functional group tolerance,and the potential for extensive downstream functionalization.The versatility of this strategy is further demonstrated by its successful application in the post-synthetic modification of complex pharmaceutical intermediates and its scalability via continuous-flow technology,underscoring its broad utility in synthetic chemistry and pharmaceutical development.
基金supported by the National Natural Science Foundation of China(51690150,51690154,21674103,51673179)International S&T Cooperation Program of China of MOST(2016YFE0129700)
文摘Polymer chain architectures play a crucial role in the physical properties of polymers and this unique phenomenon has been recognized as the topological effects.As one of the most representative architectures,macrocyclic polymers characterized by the endless topology have received extensive attention due to their distinct physical properties as compared to the linear counterparts.To understand these differences and unravel the underlying mechanisms,there is a long pursuit to efficiently fabricate macrocyclic polymers.To date,both ring-closing and ring-expansion strategies have been developed,which drastically elevates the accessibility of macrocyclic polymers.The improved availability of macrocyclic polymers enables the further investigation of the biomedical applications and the preliminary results suggest that macrocyclic polymers outperform their linear analogs in terms of improving gene delivery efficiency,elevating blood circulation time,and enhancing colloidal stability of nanoparticles.
基金Support by the National Natural Science Foundation of China(Nos.22271244 and 22071211)the Hunan Provincial Natural Science Foundation of China(Nos.2023JJ40561 and 2022JJ40359)+1 种基金the Hunan Provincial Health Commission Foundation(B202313020111)Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(No.2022C02)is gratefully acknowledged.
文摘The Pictet-Spengler/transamination cascade reaction enables modular synthesis of marinoquinoline analoviphrough three-component indole ring-expansion/cyclization in the manner of novel N1–C2 cleavage of indoles.This metal-free protocol exhibits very broad functional group tolerance with up to quantitative yields. Preliminarystudies on the antitumor activity of the resultant marinoquinoline analogues reveal that the indolyl-attachedpyrrolo[2,3-c]quinoline product (5d) shows great potential (IC50 of 0.32 μg/mL to HeLa cells) as a promisinganticancer agent in clinic.
