Efficient and modular synthesis of structurally diverse 1,4-diketones from readily available building blocks represents an essential but challenging task in organic chemistry.Herein,we report a multi-component,regiose...Efficient and modular synthesis of structurally diverse 1,4-diketones from readily available building blocks represents an essential but challenging task in organic chemistry.Herein,we report a multi-component,regioselective bis-acylation of olefins by merging NHC organocatalysis and photoredox catalysis.With this protocol,a broad range of 1,4-diketones could be rapidly assembled using bench-stable feedstock materials.The robustness of this method was further evaluated by sensitivity screening,and good reproductivity was observed.Moreover,the diketone products could be readily converted into functionalized heterocycles,such as multi-substituted furan,pyrrole,and pyridazine.Mechanistic investigations shed light on the NHC and photoredox dual catalytic radical reaction mechanism.展开更多
The extraction behaviors of zinc from ammoniacal solutions were investigated using β-diketone （HA） and their mixtures with CYANEX923 or LIX84I. The effects of pH, total ammonia concentration, extractant concentrati...The extraction behaviors of zinc from ammoniacal solutions were investigated using β-diketone （HA） and their mixtures with CYANEX923 or LIX84I. The effects of pH, total ammonia concentration, extractant concentration, anion species and temperature on zinc extraction were examined. The synergistic mechanism was discussed with regard to the structure of extractant and the extracted zinc complexes. It is found that the increase of total ammonia concentration and pH inhibits zinc extraction for all extraction systems due to the formation of zinc ammine complexes in aqueous phase. This effect of HA with CYANEX923 is evidently smaller than that of HA with LIX84I or HA alone system. Effect of anion species on the zinc extraction by HA with CYANEX923 can be neglected, but this effect of HA alone and the mixture of HA with LIX84I decreases in the order of （NH4）2SO4 〉 NH4NO3 〉 NH4Cl.展开更多
Alkenes are ubiquitous,and the difunctionalization of alkenes represents one of the most practical approaches for the construction of value-added compounds.Dicarbonylation of alkenes provides direct access to value-ad...Alkenes are ubiquitous,and the difunctionalization of alkenes represents one of the most practical approaches for the construction of value-added compounds.Dicarbonylation of alkenes provides direct access to value-added 1,4-dicarbonyl compounds.However,selectivity control for unsymmetric 1,2-dicarbonylation is of great challenge.We herein describe NHCs and photocatalysis co-catalyzed three-component radical 1,2-dicarbonylation of alkenes by distinguishing two carbonyl groups,providing structurally diversified 1,4-diketones.Distinct properties of acyl radical and NHCs-stabilized ketyl radical contributed to selectivity control.Acyl radicals are rapidly added to alkenes delivering alkyl radicals,which undergo subsequent radicalradical cross-coupling with NHCs-stabilized ketyl-type radicals,affording 1,2-dicarbonylation products.This transformation features mild reaction conditions,broad substrate scope,and excellent selectivity,providing a general and practical approach for the dicarbonylation of olefins.展开更多
基金the National Natural Science Foundation of China(NSFC,Nos.22071011,21871031,22271028 and 82073998)Longquan Talents Program,the Science&Technology Department of Sichuan Province(Nos.2021YJ0404,2022JDRC0045 and 2023NSFSC1081)the innovative project of Chengdu University is gratefully acknowledged.
文摘Efficient and modular synthesis of structurally diverse 1,4-diketones from readily available building blocks represents an essential but challenging task in organic chemistry.Herein,we report a multi-component,regioselective bis-acylation of olefins by merging NHC organocatalysis and photoredox catalysis.With this protocol,a broad range of 1,4-diketones could be rapidly assembled using bench-stable feedstock materials.The robustness of this method was further evaluated by sensitivity screening,and good reproductivity was observed.Moreover,the diketone products could be readily converted into functionalized heterocycles,such as multi-substituted furan,pyrrole,and pyridazine.Mechanistic investigations shed light on the NHC and photoredox dual catalytic radical reaction mechanism.
基金Project (2007CB613601) supported by the National Basic Research Program of ChinaProject (CX2010B112) supported by Hunan Provincial Innovation Foundation for Postgraduate, China
文摘The extraction behaviors of zinc from ammoniacal solutions were investigated using β-diketone （HA） and their mixtures with CYANEX923 or LIX84I. The effects of pH, total ammonia concentration, extractant concentration, anion species and temperature on zinc extraction were examined. The synergistic mechanism was discussed with regard to the structure of extractant and the extracted zinc complexes. It is found that the increase of total ammonia concentration and pH inhibits zinc extraction for all extraction systems due to the formation of zinc ammine complexes in aqueous phase. This effect of HA with CYANEX923 is evidently smaller than that of HA with LIX84I or HA alone system. Effect of anion species on the zinc extraction by HA with CYANEX923 can be neglected, but this effect of HA alone and the mixture of HA with LIX84I decreases in the order of （NH4）2SO4 〉 NH4NO3 〉 NH4Cl.
基金supported by the National Natural Science Foundation of China (22001157,21831002,22193012)the Ten Thousand Talents Program+2 种基金the Fundamental Research Funds for the Central Universities (2412022QD016,2412021QD007)the Natural Science Foundation of Jilin Province (YDZJ202201ZYTS338)the Natural Science Foundation of Shaanxi Province (2020JQ-404)
文摘Alkenes are ubiquitous,and the difunctionalization of alkenes represents one of the most practical approaches for the construction of value-added compounds.Dicarbonylation of alkenes provides direct access to value-added 1,4-dicarbonyl compounds.However,selectivity control for unsymmetric 1,2-dicarbonylation is of great challenge.We herein describe NHCs and photocatalysis co-catalyzed three-component radical 1,2-dicarbonylation of alkenes by distinguishing two carbonyl groups,providing structurally diversified 1,4-diketones.Distinct properties of acyl radical and NHCs-stabilized ketyl radical contributed to selectivity control.Acyl radicals are rapidly added to alkenes delivering alkyl radicals,which undergo subsequent radicalradical cross-coupling with NHCs-stabilized ketyl-type radicals,affording 1,2-dicarbonylation products.This transformation features mild reaction conditions,broad substrate scope,and excellent selectivity,providing a general and practical approach for the dicarbonylation of olefins.
