Our present study unveils a new and efficient N-heterocyclic carbene(NHC)-boryl radical-catalyzed cycloisomerization of N-(2-ethynylaryl)arylamides.This catalytic process is triggered by the addition of an NHC-boryl r...Our present study unveils a new and efficient N-heterocyclic carbene(NHC)-boryl radical-catalyzed cycloisomerization of N-(2-ethynylaryl)arylamides.This catalytic process is triggered by the addition of an NHC-boryl radical to the alkynyl moiety,followed by a radical cascade comprising of an intramolecular cyclization,successive 1,5-and 1,2-aryl migrations,and the reorganization of a C–C triple bond.展开更多
Due to the innate highly reactive properties and short life-time,organic free radicals can often serve as promoters or intermediates to engage in various radical transformations,which are often otherwise difficult to ...Due to the innate highly reactive properties and short life-time,organic free radicals can often serve as promoters or intermediates to engage in various radical transformations,which are often otherwise difficult to access by ionic pathway-based mechanisms.With the evolvement of radical chemistry,chiral radical catalyzed-transformations have recently emerged as an attractive and robust platform for synthesis of chiral molecules of interest.Herein,we highlight several creative and strategic advances in chiral radical catalyst design,cyclization reaction achievements,and future challenges.展开更多
Transition metal-mediated atom transfer radical polymerization (ATRP) is a "living"Jcontrolled radical polymerization. Recently, there has been widely increasing interest in reducing the high costs of catalyst sep...Transition metal-mediated atom transfer radical polymerization (ATRP) is a "living"Jcontrolled radical polymerization. Recently, there has been widely increasing interest in reducing the high costs of catalyst separation and post-polymerization purification in ATRP. In this work, trolamine was found to significantly enhance the catalytical performance of CuBr]N,N,N',N'-tetrakis(2-pyridylmethyl) ethyle- nediamine (CuBr/TPEN) and CuBr/tris[2-(dimethylamino) ethylamine] (CuBr/MesTREN). With the addition of 25-fold molar amount of trolamine relative to CuBr, the catalyst loadings of CuBr/TPEN and CuBr/Me6TREN were dramatically reduced from a catalyst-to-initiator ratio of 1 to 0.01 and 0.05, respectively. The polymerizations of methyl acrylate, methyl methacrylate and styrene still showed first-order kinetics in the presence of trolamine and produced poly(methyl acrylate), poly(methyl methacrylate) and polystyrene with molecular weights close to theoretical values and low polydispersities. These results indicate that trolamine is a highly effective and versatile promoter for ATRP and is promising for potential industrial application.展开更多
The fluoroalkyl fragment plays a vital role in various fields such as pharmaceuticals and materials science, and has a significant impact on human life not only on the present but also in the future. The insertion of ...The fluoroalkyl fragment plays a vital role in various fields such as pharmaceuticals and materials science, and has a significant impact on human life not only on the present but also in the future. The insertion of fluoroalkyl groups into the chemical skeletons can cause considerable alternations in the chemical, physical and biological properties of molecules, which has attracted numerous scientists from different fields. This review focuses on N-heterocyclic carbene(NHC)-catalyzed fluoroalkylation reactions, providing a detailed analysis and summary of the achievements in the past two decades. Many successful examples clearly indicate that NHCs can catalyze the tranformation of fluoroalkylation reagents with various electronic characteristics, whether electrophilic, nucleophilic, or radical precursors. Herein, the fluoroalkylation reactions are classified based on different catalytic modes of NHCs: Lewis base catalysis, Umploung catalysis, radical catalysis and others. Meanwhile, by refining and systematically studying the contribution of NHC catalysis in fluoroalkylation reactions, this review is expected to provide valuable insights and enlightenment for related fields.展开更多
Bimetallic Fe-Co/GAC (granular activated carbon) was prepared and used as heterogeneous catalyst in the ultrasound enhanced heterogeneous activation of peroxydisulfate (PS, S2O8 2-) process. The effect of initial ...Bimetallic Fe-Co/GAC (granular activated carbon) was prepared and used as heterogeneous catalyst in the ultrasound enhanced heterogeneous activation of peroxydisulfate (PS, S2O8 2-) process. The effect of initial pH, PS concentration, catalyst addition and stirring rate on the decolorization of Acid Orange 7 (AO7) was investigated. The results showed that the decolorization efficiency increased with an increase in PS concentration from 0.3 to 0.5 g/L and an increase in catalyst amount from 0.5 to 0.8 g/L. But further increase in PS concentration and catalyst addition would result in an unpronounced increase in decolorization efficiency. In the range of 300 to 900 r/min, stirring rate had little effect on AO7 decolorization. The catalyst stability was evaluated by measuring decolorization efficiency for four successive cycles.展开更多
基金This work was supported by the National Natural Science Foundation of China(21672195 and 21702201)the Fundamental Research Funds for the Central Univer-sitiesthe University of Science and Technology of China.
文摘Our present study unveils a new and efficient N-heterocyclic carbene(NHC)-boryl radical-catalyzed cycloisomerization of N-(2-ethynylaryl)arylamides.This catalytic process is triggered by the addition of an NHC-boryl radical to the alkynyl moiety,followed by a radical cascade comprising of an intramolecular cyclization,successive 1,5-and 1,2-aryl migrations,and the reorganization of a C–C triple bond.
基金support from the National Natural Science Foundation of China(Nos.22301109 and 22171099)the Research Funds for Talent Introduction of Jiangsu Ocean University(No.KQ23065)+1 种基金Lianyungang Haiyan Project(No.KK24005)Postgraduate Research&Practice Innovation Program of JiangsuProvince.
文摘Due to the innate highly reactive properties and short life-time,organic free radicals can often serve as promoters or intermediates to engage in various radical transformations,which are often otherwise difficult to access by ionic pathway-based mechanisms.With the evolvement of radical chemistry,chiral radical catalyzed-transformations have recently emerged as an attractive and robust platform for synthesis of chiral molecules of interest.Herein,we highlight several creative and strategic advances in chiral radical catalyst design,cyclization reaction achievements,and future challenges.
基金supported by National Natural Science Foundation of China (No.21174133)Zhejiang Science Foundation for Distinguished Young Scholars (No.LR12B04002)
文摘Transition metal-mediated atom transfer radical polymerization (ATRP) is a "living"Jcontrolled radical polymerization. Recently, there has been widely increasing interest in reducing the high costs of catalyst separation and post-polymerization purification in ATRP. In this work, trolamine was found to significantly enhance the catalytical performance of CuBr]N,N,N',N'-tetrakis(2-pyridylmethyl) ethyle- nediamine (CuBr/TPEN) and CuBr/tris[2-(dimethylamino) ethylamine] (CuBr/MesTREN). With the addition of 25-fold molar amount of trolamine relative to CuBr, the catalyst loadings of CuBr/TPEN and CuBr/Me6TREN were dramatically reduced from a catalyst-to-initiator ratio of 1 to 0.01 and 0.05, respectively. The polymerizations of methyl acrylate, methyl methacrylate and styrene still showed first-order kinetics in the presence of trolamine and produced poly(methyl acrylate), poly(methyl methacrylate) and polystyrene with molecular weights close to theoretical values and low polydispersities. These results indicate that trolamine is a highly effective and versatile promoter for ATRP and is promising for potential industrial application.
基金supported by the National Natural Science Foundation of China (21871160, 21672121, 22071130)the Bayer Investigator Fellowthe Fellowship of Tsinghua-Peking Center for Life Sciences (CLS)。
文摘The fluoroalkyl fragment plays a vital role in various fields such as pharmaceuticals and materials science, and has a significant impact on human life not only on the present but also in the future. The insertion of fluoroalkyl groups into the chemical skeletons can cause considerable alternations in the chemical, physical and biological properties of molecules, which has attracted numerous scientists from different fields. This review focuses on N-heterocyclic carbene(NHC)-catalyzed fluoroalkylation reactions, providing a detailed analysis and summary of the achievements in the past two decades. Many successful examples clearly indicate that NHCs can catalyze the tranformation of fluoroalkylation reagents with various electronic characteristics, whether electrophilic, nucleophilic, or radical precursors. Herein, the fluoroalkylation reactions are classified based on different catalytic modes of NHCs: Lewis base catalysis, Umploung catalysis, radical catalysis and others. Meanwhile, by refining and systematically studying the contribution of NHC catalysis in fluoroalkylation reactions, this review is expected to provide valuable insights and enlightenment for related fields.
基金supported by the National Natural Science Foundation of China (No. 20977069, 21211130108)the Natural Science Foundation of Hubei Province, China through "The Outstanding Youth Scholars Program" (No. 2007ABB028)
文摘Bimetallic Fe-Co/GAC (granular activated carbon) was prepared and used as heterogeneous catalyst in the ultrasound enhanced heterogeneous activation of peroxydisulfate (PS, S2O8 2-) process. The effect of initial pH, PS concentration, catalyst addition and stirring rate on the decolorization of Acid Orange 7 (AO7) was investigated. The results showed that the decolorization efficiency increased with an increase in PS concentration from 0.3 to 0.5 g/L and an increase in catalyst amount from 0.5 to 0.8 g/L. But further increase in PS concentration and catalyst addition would result in an unpronounced increase in decolorization efficiency. In the range of 300 to 900 r/min, stirring rate had little effect on AO7 decolorization. The catalyst stability was evaluated by measuring decolorization efficiency for four successive cycles.