Tetrazole-l-acetic acid was found to serve as a superior ligand for Cul-catalyzed N-arylation of imidazoles with aryl iodides under a low catalyst loading （5 mol% of Cul）. A variety of aryl iodides could he aminated...Tetrazole-l-acetic acid was found to serve as a superior ligand for Cul-catalyzed N-arylation of imidazoles with aryl iodides under a low catalyst loading （5 mol% of Cul）. A variety of aryl iodides could he aminated to provide the N-arylated products in good to excellent yields without the need of an inert atmosphere.展开更多
In the presence of CrC13 /Fe bimetal couple,per(poly)fluoroalkyl iodides add to vinyl cyclopropane compounds giving addition-ring-opening products in good yields.
(CH_3OCH_2CH_2C_5H_4)_2LnI(Ln=La,Nd)complexes have been synthesized by the reaction between NaI and[(CH_3OCH_2CH_2C_5H_4)_2LnCl]2 in THF;A single crystal X-ray study has shown that the lanthanum complex is an unsolvat...(CH_3OCH_2CH_2C_5H_4)_2LnI(Ln=La,Nd)complexes have been synthesized by the reaction between NaI and[(CH_3OCH_2CH_2C_5H_4)_2LnCl]2 in THF;A single crystal X-ray study has shown that the lanthanum complex is an unsolvated monomer with lanthanum(Ⅲ)in a trigonal bipyramidal coordination geometry if the cyclopentadienyl ring is regarded as occupying a single polyhedral vertex.展开更多
Initiated by CP_2TiCl_2/Fe redox system,2-halotetrafluoroethyl iodides readily reacted with alkynes or alkenes to give 1:1 adducts in good to excellent yields.
perfluoroalkyl iodides reacted with alkenes in acetonitrile solu- tion containing catalytic amount of organophosphine under mild condition to give the corresponding adducts in moderate to good yields.Reaction was show...perfluoroalkyl iodides reacted with alkenes in acetonitrile solu- tion containing catalytic amount of organophosphine under mild condition to give the corresponding adducts in moderate to good yields.Reaction was shown to involve a free radical mechanism.展开更多
Functionalized alkylzinc iodides will undergo 1,4-conjugation reaction with derivatives of β-nitrostyrene in the presence of Cu(OAc)2/LiCl to afford a polyfunctional nitro-compound in high yield.
Stereoselective transformation of Baylis-Hillman acetates I into corresponding （Z）-allyl iodides 2 has been achieved by treatment of I with samarium triiodide in THF. Remarkable rate acceleration of samarium triiodi...Stereoselective transformation of Baylis-Hillman acetates I into corresponding （Z）-allyl iodides 2 has been achieved by treatment of I with samarium triiodide in THF. Remarkable rate acceleration of samarium triiodide-mediated iodination of 1 was found when ionic liquid 1-n-butyl-3-methyl-imidazolium tetrafluroborate （[bmim]BF4） was used as reaction media in stead of THF. This novel approach proceeds readily at 50 ℃ within a few minutes to afford （Z）-allyl iodides 2 in excellent yields. A mechanism involving stereoselective iodination of the acetates of Baylis-Hillman adducts by samarium triiodide is described, in which a six-membered ring transition state played a key role in the stereoselective formation of 2.展开更多
An operationally simple and inexpensive catalyst system was developed for the cross coupling of potassium thiocyanate with aryl iodides by using CuI as catalyst, 1, 10-phenanthroline as ligand, and tetraethylammonium ...An operationally simple and inexpensive catalyst system was developed for the cross coupling of potassium thiocyanate with aryl iodides by using CuI as catalyst, 1, 10-phenanthroline as ligand, and tetraethylammonium iodide as activator. The procedure is applicable for the synthesis of diverse aryl thiocyanates without any exotic, poisonous reagents.展开更多
Reaction of polystyrene-supported lithium selenide with 3-acetoxy-2-methylene-alkanoates afforded the corresponding allyl selenide resins and subsequent cleavage from the polymer by treating with methyl iodide to furn...Reaction of polystyrene-supported lithium selenide with 3-acetoxy-2-methylene-alkanoates afforded the corresponding allyl selenide resins and subsequent cleavage from the polymer by treating with methyl iodide to furnish （Z）-allyl iodides in good yields and high purities. The polymeric selenium reagent can be regenerated and reused. So it is a environmentally benign reagent.展开更多
The valorization of nitrous oxide(N_(2)O)as an oxygen atom donor presents an attractive opportunity for green chemistry applications,leveraging both its industrial abundance and thermodynamically favorable oxidation p...The valorization of nitrous oxide(N_(2)O)as an oxygen atom donor presents an attractive opportunity for green chemistry applications,leveraging both its industrial abundance and thermodynamically favorable oxidation potential.However,practical implementation has been constrained by the inherent kinetic inertness and poor coordinating ability of N_(2)O.While prior studies achieved N_(2)O-mediated conversion of aryl halides to phenols,such transformations necessitated stoichiometric chemical reductants and elevated pressure(2 atm),posing challenges in operational safety and process scalability.This study focuses on an electrochemical strategy that enables efficient oxygen atom transfer under ambient pressure through controlled current application.This methodology facilitates the selective transformation of aryl iodides to phenols without external reducing agents,establishing an environmentally benign synthetic pathway.By replacing traditional chemical reductants with electrons as the sole reducing equivalent,our approach addresses critical sustainability challenges in aromatic oxygenation chemistry while maintaining operational simplicity under mild conditions.展开更多
We herein present an efficient denitrative iodination method of(hetero)nitroarenes mediated by commercially available and cost-effective hydroiodic acid(HI).During the reaction process,HI plays its dual roles as both ...We herein present an efficient denitrative iodination method of(hetero)nitroarenes mediated by commercially available and cost-effective hydroiodic acid(HI).During the reaction process,HI plays its dual roles as both the sustainable reductant of nitro group and iodine source in the iodination step,which successfully integrates three steps into a one-pot procedure and significantly simplifies the reaction system.This approach enables a smooth metal-free conversion of nitroarenes to corresponding aryl iodides via one-pot process,exhibits a broad substrate scope and good reaction efficiency,and was conveniently applied in the concise synthesis of pharmaceuticals.展开更多
Herein,we report the first electrochemical strategy for the borylation of aryl iodides via a radical pathway using current as a driving force.A mild reaction condition allows an assorted range of readily available ary...Herein,we report the first electrochemical strategy for the borylation of aryl iodides via a radical pathway using current as a driving force.A mild reaction condition allows an assorted range of readily available aryl iodides to be proficiently converted into synthetically valuable arylboronic esters under transition metal catalyst-free conditions.Moreover,this method also shows good functional group tolerance.Initial control mechanistic experiments reveal the formation of aryl radical as a key intermediate and the current plays an important role in the generation of radical intermediate.展开更多
Amino acid precursors in protected amino alcohol form are important synthons that can be used as building-blocks for the hemisynthesis of non-natural amino acids.Serine can be used as a common starting material for th...Amino acid precursors in protected amino alcohol form are important synthons that can be used as building-blocks for the hemisynthesis of non-natural amino acids.Serine can be used as a common starting material for the synthesis of such compounds differently protected.Particularly,protected amino alcohols bearing an ethynyl and/or an iodoethynyl group can be used in cross-couplings,in 1,3-dipolar cycloadditions and/or in Nozaki-Hiyama-Kishi type reactions.We thus demonstrated that the efficiently protected amino alcohols derived from serine can be coupled to a sugar derivative by an indium mediated alkynylation reaction.The conditions of this coupling are compatible with such functionalized derivatives and allow envisaging an access to C-glycosylated amino acids.展开更多
The sodium-iodine(Na-I)battery exhibits significant potential as an alternative energy storage device to the lithium-ion battery.However,its development is hindered by inadequate electrical and thermal stability,as we...The sodium-iodine(Na-I)battery exhibits significant potential as an alternative energy storage device to the lithium-ion battery.However,its development is hindered by inadequate electrical and thermal stability,as well as the dissolution and shuttling of polyiodide.In this study,we report a preparation method for melamine carbon sponge(MC)via carbonizing a commercially available kitchen sponge.It was revealed that the as-prepared MC,composed of unique self-growing carbon nanotubes,could provide both physical and chemical adsorption capabilities for intermediate polyiodides to improve the electrochemical performance of NaI.Consequently,the NaI/MC electrode effectively minimized polyiodide dissolution and reduced the electrochemical impedance.The NaI/MC cathode demonstrated a high average discharge capacity of 92.75 mAh·g^(–1)over 200 cycles while maintaining a coulombic efficiency of 94%.The research findings from our study have promising applications in Na-I batteries.展开更多
Properties of trivalent rare earth ions have been extensively understood. Besidesthe +3 valent state, the rare earth elements also have +4, +2 and +1 valencies,clusters and mixture valent compounds. The research of th...Properties of trivalent rare earth ions have been extensively understood. Besidesthe +3 valent state, the rare earth elements also have +4, +2 and +1 valencies,clusters and mixture valent compounds. The research of their synthesis, structure,properties of unusual valent rare earth compounds has theoretical and practicalsignificance. It will broaden the horizon of rare earth chemistry and extend展开更多
A new copper and silver-mediated cyanation of aryl iodides with DDQ as a cyanide source is achieved, provid- ing nitriles with good yields. This new approach represents a safe method leading to aryl nitriles.
2-Polyfluoroalkyl quinoline derivatives were synthesized from the enaminones which were obtained from the reaction of FT-aryl polyfluoroalkyl imidoyl iodides with methyl ketones.
Perovskite solar cells(PSCs)based onα-phase FAPbI_(3)(α-FAPbI_(3))microcrystals precursor outperform those withδ-phase mi-crocrystals due to their superior crystallinity and fewer defects,makingα-phase microcrysta...Perovskite solar cells(PSCs)based onα-phase FAPbI_(3)(α-FAPbI_(3))microcrystals precursor outperform those withδ-phase mi-crocrystals due to their superior crystallinity and fewer defects,makingα-phase microcrystals precursor more advantageous for high-per-formance PSCs.However,most reported synthesis methods of perovskite microcrystals,especially for aqueous synthesis,fail to reach the energy threshold required forα-phase transformation and therefore exhibit theδphase.In this study,we introduce a novel aqueous syn-thesis method to fabricateα-FAPbI_(3) microcrystals.Our approach overcomes the energy barrier by properly heating the reaction system,enabling the direct formation ofα-FAPbI_(3) in water.This direct one-step aqueous synthesis route yieldsα-FAPbI_(3) microcrystals with su-perior phase purity,crystallinity,and minimal defect density.Combined with green anti-solvent,the high-qualityα-FAPbI_(3) microcrystals serving as exceptional precursors endow perovskite films with reduced nonradiative recombination.The PSC achieves a remarkable power conversion efficiency(PCE)of 24.43%,which is one of the highest PCE reports for using the green anti-solvent in ambient air condition.This aqueous synthesis approach shows a significant potential for scalable production of high-performance PSCs.展开更多
Poly(3-hexylthiophene)(P3HT)has been used in CsPbI_(3)per-ovskite solar cells(PSCs)as the hole transport layer(HTL),due to its excellent hydrophobic prop-erty and cheap cost.However,the inevitable defects in perovskit...Poly(3-hexylthiophene)(P3HT)has been used in CsPbI_(3)per-ovskite solar cells(PSCs)as the hole transport layer(HTL),due to its excellent hydrophobic prop-erty and cheap cost.However,the inevitable defects in perovskite lead to the limited photovoltaic performance of CsPbI_(3)PSCs.In this study,diethylammonium io-dide(DEAI)was doped as an ad-ditive to passivate the defects in P3HT based CsPbI_(3)perovskite.Considering the diethylamine cations can effectively form hydrogen bonds with halide ion,the DEAI doping method could not only reduce the defect density but also facilitate the extraction and transport of carriers in the device.The optimal power conversion efficiency of the device prepared with DEAI doping method increases from 14.68%to 16.75%.In addition,the stability of the device is also signifi-cantly upgraded due to the improvement of CsPbI_(3)perovskite film.This work can provide re-liable theoretical and experimental evidence for further PSCs research.展开更多
基金supported fnancially by the National Basic Research Program of China(973 Program,No.2012CB722603)the Start-Up Foundation for Young Scientists of Shihezi University(Nos.RCZX201012,RCZX201014,RCZX201015)
文摘Tetrazole-l-acetic acid was found to serve as a superior ligand for Cul-catalyzed N-arylation of imidazoles with aryl iodides under a low catalyst loading （5 mol% of Cul）. A variety of aryl iodides could he aminated to provide the N-arylated products in good to excellent yields without the need of an inert atmosphere.
文摘In the presence of CrC13 /Fe bimetal couple,per(poly)fluoroalkyl iodides add to vinyl cyclopropane compounds giving addition-ring-opening products in good yields.
文摘(CH_3OCH_2CH_2C_5H_4)_2LnI(Ln=La,Nd)complexes have been synthesized by the reaction between NaI and[(CH_3OCH_2CH_2C_5H_4)_2LnCl]2 in THF;A single crystal X-ray study has shown that the lanthanum complex is an unsolvated monomer with lanthanum(Ⅲ)in a trigonal bipyramidal coordination geometry if the cyclopentadienyl ring is regarded as occupying a single polyhedral vertex.
文摘Initiated by CP_2TiCl_2/Fe redox system,2-halotetrafluoroethyl iodides readily reacted with alkynes or alkenes to give 1:1 adducts in good to excellent yields.
文摘perfluoroalkyl iodides reacted with alkenes in acetonitrile solu- tion containing catalytic amount of organophosphine under mild condition to give the corresponding adducts in moderate to good yields.Reaction was shown to involve a free radical mechanism.
文摘Functionalized alkylzinc iodides will undergo 1,4-conjugation reaction with derivatives of β-nitrostyrene in the presence of Cu(OAc)2/LiCl to afford a polyfunctional nitro-compound in high yield.
基金Project (No. 2004C21032) supported by the Key Technology R & DProgram of Zhejiang Province, China
文摘Stereoselective transformation of Baylis-Hillman acetates I into corresponding （Z）-allyl iodides 2 has been achieved by treatment of I with samarium triiodide in THF. Remarkable rate acceleration of samarium triiodide-mediated iodination of 1 was found when ionic liquid 1-n-butyl-3-methyl-imidazolium tetrafluroborate （[bmim]BF4） was used as reaction media in stead of THF. This novel approach proceeds readily at 50 ℃ within a few minutes to afford （Z）-allyl iodides 2 in excellent yields. A mechanism involving stereoselective iodination of the acetates of Baylis-Hillman adducts by samarium triiodide is described, in which a six-membered ring transition state played a key role in the stereoselective formation of 2.
文摘An operationally simple and inexpensive catalyst system was developed for the cross coupling of potassium thiocyanate with aryl iodides by using CuI as catalyst, 1, 10-phenanthroline as ligand, and tetraethylammonium iodide as activator. The procedure is applicable for the synthesis of diverse aryl thiocyanates without any exotic, poisonous reagents.
基金the National Natural Science Foundation of China （No. 20562005） NSF of Jiangxi Province （No. 0620021） for financial support.
文摘Reaction of polystyrene-supported lithium selenide with 3-acetoxy-2-methylene-alkanoates afforded the corresponding allyl selenide resins and subsequent cleavage from the polymer by treating with methyl iodide to furnish （Z）-allyl iodides in good yields and high purities. The polymeric selenium reagent can be regenerated and reused. So it is a environmentally benign reagent.
基金National Natural Science Foundation of China(Project No.:52320105003,Project No.:52303019)the CAS-ANSO Co-funding Research Project(Project No.:CAS-ANSO-CF-2024)+2 种基金the National Key R&D Program of China(Project No.:2023YFC3707201)the Fundamental Research Funds for the Central Universities(Project No.:E3ET1803)China Postdoctoral Science Foundation(Project No:2024T170904)。
文摘The valorization of nitrous oxide(N_(2)O)as an oxygen atom donor presents an attractive opportunity for green chemistry applications,leveraging both its industrial abundance and thermodynamically favorable oxidation potential.However,practical implementation has been constrained by the inherent kinetic inertness and poor coordinating ability of N_(2)O.While prior studies achieved N_(2)O-mediated conversion of aryl halides to phenols,such transformations necessitated stoichiometric chemical reductants and elevated pressure(2 atm),posing challenges in operational safety and process scalability.This study focuses on an electrochemical strategy that enables efficient oxygen atom transfer under ambient pressure through controlled current application.This methodology facilitates the selective transformation of aryl iodides to phenols without external reducing agents,establishing an environmentally benign synthetic pathway.By replacing traditional chemical reductants with electrons as the sole reducing equivalent,our approach addresses critical sustainability challenges in aromatic oxygenation chemistry while maintaining operational simplicity under mild conditions.
基金the National Key Research and Development Project(No.2023YFF1205103)the National Natural Science Foundation of China(No.22371007)the Peking University Medicine plus X Pilot Program-Key Technologies R&D Project(No.2024YXXLHGG001)for financial support。
文摘We herein present an efficient denitrative iodination method of(hetero)nitroarenes mediated by commercially available and cost-effective hydroiodic acid(HI).During the reaction process,HI plays its dual roles as both the sustainable reductant of nitro group and iodine source in the iodination step,which successfully integrates three steps into a one-pot procedure and significantly simplifies the reaction system.This approach enables a smooth metal-free conversion of nitroarenes to corresponding aryl iodides via one-pot process,exhibits a broad substrate scope and good reaction efficiency,and was conveniently applied in the concise synthesis of pharmaceuticals.
基金the National Natural Science Foundation of China(Grant No.21772003).
文摘Herein,we report the first electrochemical strategy for the borylation of aryl iodides via a radical pathway using current as a driving force.A mild reaction condition allows an assorted range of readily available aryl iodides to be proficiently converted into synthetically valuable arylboronic esters under transition metal catalyst-free conditions.Moreover,this method also shows good functional group tolerance.Initial control mechanistic experiments reveal the formation of aryl radical as a key intermediate and the current plays an important role in the generation of radical intermediate.
文摘Amino acid precursors in protected amino alcohol form are important synthons that can be used as building-blocks for the hemisynthesis of non-natural amino acids.Serine can be used as a common starting material for the synthesis of such compounds differently protected.Particularly,protected amino alcohols bearing an ethynyl and/or an iodoethynyl group can be used in cross-couplings,in 1,3-dipolar cycloadditions and/or in Nozaki-Hiyama-Kishi type reactions.We thus demonstrated that the efficiently protected amino alcohols derived from serine can be coupled to a sugar derivative by an indium mediated alkynylation reaction.The conditions of this coupling are compatible with such functionalized derivatives and allow envisaging an access to C-glycosylated amino acids.
基金supported by Shenzhen Key Laboratory of Advanced Functional Carbon Materials Research and Comprehensive Application(Grant No.ZDSYS20220527171407017).
文摘The sodium-iodine(Na-I)battery exhibits significant potential as an alternative energy storage device to the lithium-ion battery.However,its development is hindered by inadequate electrical and thermal stability,as well as the dissolution and shuttling of polyiodide.In this study,we report a preparation method for melamine carbon sponge(MC)via carbonizing a commercially available kitchen sponge.It was revealed that the as-prepared MC,composed of unique self-growing carbon nanotubes,could provide both physical and chemical adsorption capabilities for intermediate polyiodides to improve the electrochemical performance of NaI.Consequently,the NaI/MC electrode effectively minimized polyiodide dissolution and reduced the electrochemical impedance.The NaI/MC cathode demonstrated a high average discharge capacity of 92.75 mAh·g^(–1)over 200 cycles while maintaining a coulombic efficiency of 94%.The research findings from our study have promising applications in Na-I batteries.
基金Project supported by the National Natural Science Foundation of China the Chemical Laboratory on Rare Earth Elements, Changchun Institute of Applied Chemistry, Academia Sinica.
文摘Properties of trivalent rare earth ions have been extensively understood. Besidesthe +3 valent state, the rare earth elements also have +4, +2 and +1 valencies,clusters and mixture valent compounds. The research of their synthesis, structure,properties of unusual valent rare earth compounds has theoretical and practicalsignificance. It will broaden the horizon of rare earth chemistry and extend
基金We thank the National Natural Science Foundation of China （No. 21272178）, the Natural Science Founda- tion of Zhejiang Province （Nos. R4110294 and LY12B02010）.
文摘A new copper and silver-mediated cyanation of aryl iodides with DDQ as a cyanide source is achieved, provid- ing nitriles with good yields. This new approach represents a safe method leading to aryl nitriles.
基金Project partially supported by the National Natural Science Foundation of China(No:29632003).
文摘2-Polyfluoroalkyl quinoline derivatives were synthesized from the enaminones which were obtained from the reaction of FT-aryl polyfluoroalkyl imidoyl iodides with methyl ketones.
基金financially supported by the National Key Research and Development Program of China(No.2022YFB3803300)the Major Scientific and Technological Project in 2022 of Changsha,China(No.kq2301002).
文摘Perovskite solar cells(PSCs)based onα-phase FAPbI_(3)(α-FAPbI_(3))microcrystals precursor outperform those withδ-phase mi-crocrystals due to their superior crystallinity and fewer defects,makingα-phase microcrystals precursor more advantageous for high-per-formance PSCs.However,most reported synthesis methods of perovskite microcrystals,especially for aqueous synthesis,fail to reach the energy threshold required forα-phase transformation and therefore exhibit theδphase.In this study,we introduce a novel aqueous syn-thesis method to fabricateα-FAPbI_(3) microcrystals.Our approach overcomes the energy barrier by properly heating the reaction system,enabling the direct formation ofα-FAPbI_(3) in water.This direct one-step aqueous synthesis route yieldsα-FAPbI_(3) microcrystals with su-perior phase purity,crystallinity,and minimal defect density.Combined with green anti-solvent,the high-qualityα-FAPbI_(3) microcrystals serving as exceptional precursors endow perovskite films with reduced nonradiative recombination.The PSC achieves a remarkable power conversion efficiency(PCE)of 24.43%,which is one of the highest PCE reports for using the green anti-solvent in ambient air condition.This aqueous synthesis approach shows a significant potential for scalable production of high-performance PSCs.
基金supported by the National Natural Scientific Foundation of China(No.62305243)Fundamental Research Program of Shanxi Province(Nos.20210302124629,20210302124163,20210302124392,202203021212217)funded by China Scholarship Council。
文摘Poly(3-hexylthiophene)(P3HT)has been used in CsPbI_(3)per-ovskite solar cells(PSCs)as the hole transport layer(HTL),due to its excellent hydrophobic prop-erty and cheap cost.However,the inevitable defects in perovskite lead to the limited photovoltaic performance of CsPbI_(3)PSCs.In this study,diethylammonium io-dide(DEAI)was doped as an ad-ditive to passivate the defects in P3HT based CsPbI_(3)perovskite.Considering the diethylamine cations can effectively form hydrogen bonds with halide ion,the DEAI doping method could not only reduce the defect density but also facilitate the extraction and transport of carriers in the device.The optimal power conversion efficiency of the device prepared with DEAI doping method increases from 14.68%to 16.75%.In addition,the stability of the device is also signifi-cantly upgraded due to the improvement of CsPbI_(3)perovskite film.This work can provide re-liable theoretical and experimental evidence for further PSCs research.
