A highly efficient and mild method for[3 t 2]cycloaddition ofβ-sulfonyl-α,β-unsaturated ketones with terminal allenoates was well-explored and developed.The reactions were successfully performed by applying multifu...A highly efficient and mild method for[3 t 2]cycloaddition ofβ-sulfonyl-α,β-unsaturated ketones with terminal allenoates was well-explored and developed.The reactions were successfully performed by applying multifunctional chiral phosphine P6 which was screened from eight chiral phosphorus reagents to finally result in a variety of enantioenriched sulfone-substituted cyclopentenes with two chiral centers(up to 81%yield with 94%ee).Moreover,2.5 mol%catalytic equivalents were proved to be feasible when this reaction was performed on a 10 mmol scale.展开更多
A new class of m-hydroxybenzyl alcohols has been designed as competent three-carbon building blocks and achieved their applica-tion in 2-indolylmethanol-involved regioselective(3+3)cycloadditions under the catalysis o...A new class of m-hydroxybenzyl alcohols has been designed as competent three-carbon building blocks and achieved their applica-tion in 2-indolylmethanol-involved regioselective(3+3)cycloadditions under the catalysis of Br?nsted acids.By this appoach,a series of indole-fused six-membered cycloadducts have been synthesized in overall good yields(up to 98%)with excellent regioselectivity(all>95:5 rr),thus affording a powerful method for the construction of indole-fused six-membered rings.Moreover,a catalytic asymmetric version of this(3+3)cycloaddition has been preliminarily investigated,which revealed the potential of the reaction for constructing chiral indole-fused six-membered rings in an enantioselective manner.This work not only has accomplished the first design of m-hydroxybenzyl alcohols as competent reactants,but also represents the first application of m-hydroxybenzyl alcohols as three-carbon building blocks in cycloadditions.In addition,this work provides a good example for regioselective and C3-nucleophilic(3+3)cycloadditions of 2-indolylmethanols,which will substantially enrich the chemistry of 2-indolylmethanols.展开更多
Comprehensive Summary Metallacyclopentadienes play a vital role in transition-metal mediated and catalyzed cycloaddition reactions of alkynes.Though versatile reactions of metallacyclopentadienes with alkynes have bee...Comprehensive Summary Metallacyclopentadienes play a vital role in transition-metal mediated and catalyzed cycloaddition reactions of alkynes.Though versatile reactions of metallacyclopentadienes with alkynes have been disclosed,[2+1]cycloadditions of metallacyclopentadienes and alkynes have never been discovered.In present work,we report the formal[2+1]cycloadditions of a metallacyclopentadiene unit with a broad scope of commercial alkynes,providing a facile strategy to construct tetracyclic conjugated compounds.The deuterated experiment indicates a metal vinylidene intermediate has been involved in[2+1]cycloaddition.Moreover,the electrophilic substitution reaction of the tetracyclic conjugated compound with the aid of density functional theory(DFT)calculated Fukui functions is investigated.展开更多
Chiral seven-membered ring systems such as seven-membered carbocycles and heterocycles are widely found in natural products and pharmaceuticals.Therefore,the catalytic enantioselective construction of such frameworks ...Chiral seven-membered ring systems such as seven-membered carbocycles and heterocycles are widely found in natural products and pharmaceuticals.Therefore,the catalytic enantioselective construction of such frameworks has evoked considerable interest in the field of chemistry.Among the various approaches,organocatalytic asymmetric(4+3)cycloadditions are highly effective for the enantioselective construction of seven-membered rings.Over the past two decades,substantial efforts have been devoted to this field and chemists have developed various organocatalytic asymmetric(4+3)cycloadditions.This review summarizes the progress in organocatalytic asymmetric(4+3)cycloadditions from 2003 to early 2022 and provides insights into challenging issues faced in this research field,enabling the future development of this field.展开更多
Subject Code:B02 With the support by the National Natural Science Foundation of China,a collaborative study by the research groups led by Prof.Chen Yingchun(陈应春)from Sichuan University and Dr.Ouyang Qin(欧阳勤)from...Subject Code:B02 With the support by the National Natural Science Foundation of China,a collaborative study by the research groups led by Prof.Chen Yingchun(陈应春)from Sichuan University and Dr.Ouyang Qin(欧阳勤)from the Third Military Medical University demonstrates switchable regioselective[6+2]。展开更多
The[8+4]cycloaddition of indene-2-carbaldehydes with indole-2,3-quinodimethanes and pyrrolidone-3,4-dienes is described,affording indole and pyrrolidone annulated bicyclo[4.2.1]nonanes in a highly peri-,diastereo-,and...The[8+4]cycloaddition of indene-2-carbaldehydes with indole-2,3-quinodimethanes and pyrrolidone-3,4-dienes is described,affording indole and pyrrolidone annulated bicyclo[4.2.1]nonanes in a highly peri-,diastereo-,and enantioselective fashion in the presence of a secondary amine catalyst.This reaction,which proceeds through catalytically generated isobenzofulvenes,represents the first asymmetric version of high-order[8+4]cycloaddition.展开更多
The development of novel synthons and efficient methods to synthesize chiral polycyclic indoles has been a hot topic in organic synthesis and medicinal chemistry owing to their broad applications in medicines,pesticid...The development of novel synthons and efficient methods to synthesize chiral polycyclic indoles has been a hot topic in organic synthesis and medicinal chemistry owing to their broad applications in medicines,pesticides,and other functional molecules.Here,we disclosed novel indolyl substituted metal-allyl zwitterionic intermediates through the decarboxylation of conveniently available vinyl indoloxazolidones,which could be regarded as two types of dipolar species through the anionic delocalization.The palladium-π-allyl species tended to serve as an all-carbon 1,3-dipole in the asymmetric[3+2]cycloaddition with electrondeficient alkenes,which furnished polysubstituted cyclopenta[b]indoles with high regio-and stereoselectivities.Meanwhile,the iridium-π-allyl species was recognized as an aza-1,3-dipole in asymmetric[3+2]cycloaddition with in situ generated C1 ammonium enolates,affording pyrrolo[1,2-α]indoles with high diastereo-and enantioselectivities.In addition,the dipolar cycloadditions could be easily scaled-up and several synthetic transformations of the cycloadducts were demonstrated for the rapid synthesis of diverse chiral polycyclic indoles.展开更多
Understanding and controlling supramolecular template effect assembly via a photochemical reaction in different solid and solution phases is one of the main topics in photochemistry. Here, an interesting case of phase...Understanding and controlling supramolecular template effect assembly via a photochemical reaction in different solid and solution phases is one of the main topics in photochemistry. Here, an interesting case of phase-mediated controllable intramolecular/intermolecular photochemical [2+2] cycloadditions assisted by supramolecular templates was demonstrated. Direct irradiation of the complexes in solution yields intramolecular photoproducts exclusively, whereas exposure of the solid powder sample under the same conditions yields intermolecular dinuclear species quantitatively. The nature of the phase and supramolecular interaction affects the geometrical arrangements of the metallacycles, leading to different cycloaddition products under photoirradiation. The crystal structures of different products were investigated by single-crystal X-ray diffraction, nuclear magnetic resonance(NMR) spectrometry, and electrospray ionization mass spectrometry(ESI-MS).展开更多
A cascade carbonylative ring expansion and [2+2]/[4+2] cycloaddition of strained 1-iminylphosphirane complexes with aryl allenes were reported.The carbonylative ring expansion of 1-iminylphosphirane complexes provides...A cascade carbonylative ring expansion and [2+2]/[4+2] cycloaddition of strained 1-iminylphosphirane complexes with aryl allenes were reported.The carbonylative ring expansion of 1-iminylphosphirane complexes provides an azaphosphacyclohexone complex intermediate with a C=P double bond.The following [2+2] or dearomatic [4+2] cycloaddition of this intermediate with allenes is modulated by the aryl substituents on the imino carbon.The regioselective [2+2] cycloaddition with 1,1-diarylallene provides an entry to bicyclo[4.2.0]octan-4-one skeletons featuring a four-membered phosphacyclobutane moiety.While dearomatic [4+2] cycloaddition was preferred with less aromatic naphthalene and yielded octahydrochrysene skeleton containing heteroatoms.展开更多
Furans bearing epoxy enolsilane units via a tether that incorporates a nitrogen heteroatom,undergo intramolecular(4+3)cycloadditions to generate bis-heteroatomic polycyclic adducts having piperidine moieties in their ...Furans bearing epoxy enolsilane units via a tether that incorporates a nitrogen heteroatom,undergo intramolecular(4+3)cycloadditions to generate bis-heteroatomic polycyclic adducts having piperidine moieties in their frameworks.The cycloadducts,ultimately derived from furfural,a renewal chemical feedstock,are obtained with up to 4:1 dr and with ee retained from the epoxide.展开更多
The first example of stereoconvergent 1,3-dipolar cycloaddition of nitrile oxides and nitrile imines with E/Z isomeric mixture of electron-deficient olefins is reported,delivering isoxazolines and pyrazolines bearing ...The first example of stereoconvergent 1,3-dipolar cycloaddition of nitrile oxides and nitrile imines with E/Z isomeric mixture of electron-deficient olefins is reported,delivering isoxazolines and pyrazolines bearing two vicinal stereogenic tertiary and trifluoromethylated quaternary carbon centers with perfect regioand diastereoselectivities.The possibility of concerted cycloaddition/epimerization sequence under basic condition to form the thermodynamically stable diastereomers is excluded through some control experiments and DFT calculations,and a stepwise mechanism is proposed.展开更多
Regiodivergent asymmetric cycloadditions from the same set of starting materials offer interesting opportunities for rapid construction of optically active cyclic molecules with structural diversity.However,this remai...Regiodivergent asymmetric cycloadditions from the same set of starting materials offer interesting opportunities for rapid construction of optically active cyclic molecules with structural diversity.However,this remains a challenging task due to the difficulty of simultaneously controlling the regio-,diastereo-,and enantioselectivity in the ring formation processes.To address this long-standing problem.展开更多
Three-membered unsaturated rings have been widely utilized in organic synthesis due to their inherent highly strained structures.Although much research has been applied to ring-expansion reactions of such strained rin...Three-membered unsaturated rings have been widely utilized in organic synthesis due to their inherent highly strained structures.Although much research has been applied to ring-expansion reactions of such strained ring systems,pathways other than[3+2]cycloadditions have rarely been observed in their reactions with alkynes,and to date,no[3+1]cycloadditions of isolated three-membered unsaturated rings with alkynes have been reported.Here we demonstrate an unprecedented[3+1]cycloaddition in which a fused metalla-azirine is used as a template to generate a series of planar CCCCX-type(X=N,O,S)pentadentate carbolong complexes 3–6.A series of substituted alkynes was tested for further exploration of the scope and mechanism for the[3+1]cycloaddition reactions.Complexes 3–6 represent rare examples of planar pentadentate complexes that assemble fourπ-conjugated fused rings by one bridgehead atom.These novel complexes are thermally stable in air and absorb ultraviolet,visible,and near-infrared light,and thus are potentially applicable in photoelectric devices and pharmaceuticals.展开更多
Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture ...Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture and conversion of CO_(2)into value-added products,such as cyclic carbonates,is booming.While CO_(2)is an abundant,cheap,non-toxic,and readily accessible Cl feedstock,its thermodynamic stability necessitates the development of highly efficient catalysts that are able to promote chemical reactions under mild conditions.In this work,a novel mesoporous poly(ionic liquid)with dual active sites was synthesized through a facile method that involves co-polymerization,post-synthetic metalation,and supercritical CO_(2)drying.Due to a high density of nucleophilic and electrophilic sites,the as-prepared poly(ionic liquid),denoted as P2D-4BrBQA-Zn,offers excellent performance in a CO_(2)cycloaddition reaction using epichlorohydrin as the substrate(98.9%conversion and 96.9%selectivity).Moreover the reaction is carried out under mild,solvent-free,and additive-free conditions.Notably,P2D-4BrBQA-Zn also efficiently promotes the conversion of various other epoxide substrates into cyclic carbonates.Overall,the catalyst is found to have excellent substrate compatibility,stability,and recyclability.展开更多
The synthesis of new indoloannulated thiopyranethiones is reported. The key-step is a rhodium-catalyzed [2 + 2 + 2]-cycloaddition of alkynyl-ynamides with carbon disulfide to close the pyrrole and the thiopyranethione...The synthesis of new indoloannulated thiopyranethiones is reported. The key-step is a rhodium-catalyzed [2 + 2 + 2]-cycloaddition of alkynyl-ynamides with carbon disulfide to close the pyrrole and the thiopyranethione rings simultaneously. A violet idolothiopyrane thione or a mixture of the violet and a red isomer result from [RhCl(C<sub>8</sub>H<sub>14</sub>)<sub>2</sub>]<sub>2</sub>/3BINAP catalyzed cycloadditions, the regiochemistry is controlled by the substitution pattern on the alkynyl-ynamide.展开更多
The cycloaddition of CO2 with epoxides catalyzed by ionic liquids(ILs)has been a widely ongoing studied hot topic over the years.Recent experimental research has shown that the protic ionic liquids(PILs)behave stronge...The cycloaddition of CO2 with epoxides catalyzed by ionic liquids(ILs)has been a widely ongoing studied hot topic over the years.Recent experimental research has shown that the protic ionic liquids(PILs)behave stronger hydrogen proton donating ability than aprotic ionic liquids(APILs),and can effectively catalyze the cycloaddition of CO2.Unfortunately,the mechanistic explanation remains primarily unraveled.Herein,a detailed simulation study on the cycloaddition reaction catalyzed by PIL([HDBU][Mim])in comparison with APIL([MeDBU][Mim])re-action catalysts was conducted,including the three-step route(ring-opening of PO(propylene oxide),insertion of CO2 and ring-closure of propylene carbonate(PC))and two-step route(simultaneously ring-opening of PO and addition of CO2,and then ring-closure of PC).Based on the activation energy barrier of the rate-determining step,PIL preferentially activates PO as the optimal route for the reaction with the energy barrier of 23.2 kcal mol-1,while that of APIL is 31.2 kcal mol-1.The role of[HDBU]+in the reaction was also explored and found that the direct formation of intermolecular hydrogen bond(H-bond)between[HDBU]+and the reactants(PO+CO2)was unfavorable for the reaction,while the cooperation with the anion[Mim]-to assist indirectly was more conducive.To fully consider the reaction microenvironment of ILs,ONIOM calculation was used to study the solvent effect.At last,the above conclusions were further verified by the analysis of intermediates with charge,non-covalent interaction(NCI),and atoms in molecules(AIM)methods.The computational findings show that ILs studied in this work have dual functions of catalyst and solvent,enabling a microscopic understanding of the ILs catalyst for CO2 utilization as well as providing guidance for the rational design of more efficient ILs-based catalysts.展开更多
A double active center system, namely Salen-Cu(Ⅱ)@MIL-101(Cr), was successfully synthesized via the"ship in a bottle" approach, which acted as a bifunctional material for both capture and conversion of CO_2...A double active center system, namely Salen-Cu(Ⅱ)@MIL-101(Cr), was successfully synthesized via the"ship in a bottle" approach, which acted as a bifunctional material for both capture and conversion of CO_2 in a single process. For the first time, Salen-Cu(Ⅱ)@MIL-101(Cr) catalyst was developed for the synthesis of propylene carbonate from CO_2 and propylene oxide under room temperature and ambient pressure with a yield of 87.8% over 60 h. Furthermore, the reaction mechanism was also discussed.展开更多
Addition reaction of Grignard’s reagent to 5-methoxy-2(5H)-furanone 1 was accomplished, which provided a new possible route for synthesizing β-alkyl-γ-alkyloxy-γ-butyrolactone. A novel concise method of preparing ...Addition reaction of Grignard’s reagent to 5-methoxy-2(5H)-furanone 1 was accomplished, which provided a new possible route for synthesizing β-alkyl-γ-alkyloxy-γ-butyrolactone. A novel concise method of preparing fused heterocyclic compounds was offered by 1,3-dipolar cycloaddition reaction of silyl nitronates to 1.展开更多
Two kinds of bi-functional transition metal doped mesoporous materials(Fe-HMS and Fe-MCM-41) are prepared using one-step hydrothermal method and then treated with hydrochloric acid ethanol solution.The N2 adsorption a...Two kinds of bi-functional transition metal doped mesoporous materials(Fe-HMS and Fe-MCM-41) are prepared using one-step hydrothermal method and then treated with hydrochloric acid ethanol solution.The N2 adsorption and HRTEM results show that both of Fe-HMS and Fe-MCM-41 possess mesoporous structure. The UV–vis results suggest that the Fe species are mainly located within the framework. The basicity of as-prepared samples was studied by temperature programmed desorption using CO2 as probe molecule(CO2-TPD). The catalytic performance of Fe-HMS and Fe-MCM-41 in CO2 cycloaddition largely depends on the amount of the accessible basic sites. The acid–base active sites, framework Fe and PDDA species cooperatively catalyze the CO2 cycloaddition for the production of cyclic carbonates under the condition without any co-catalyst. The conversion of epichlorohydrin(ECH) is 97.4% and the selectivity of chloropropene carbonate is 92.9% under optimal conditions. The approximate rate constant of cycloaddition reaction of CO2 with ECH under optimum reaction temperature is calculated. It is worth noting that the Fe-HMS material shows superior reusability than Fe-MCM-41. In addition, this work provides a facile way on the synthesis of bi-functional acid–base heterogeneous catalyst with outstanding catalytic performance for the fixation of CO2.展开更多
基金The authors are grateful to NSFC(Nos.21971066 and 21772042)for financial support.Special thanks to profJunliang Zhang(Fudan University)for his kind suggestion on this[3 t 2]cycloaddition reaction.
文摘A highly efficient and mild method for[3 t 2]cycloaddition ofβ-sulfonyl-α,β-unsaturated ketones with terminal allenoates was well-explored and developed.The reactions were successfully performed by applying multifunctional chiral phosphine P6 which was screened from eight chiral phosphorus reagents to finally result in a variety of enantioenriched sulfone-substituted cyclopentenes with two chiral centers(up to 81%yield with 94%ee).Moreover,2.5 mol%catalytic equivalents were proved to be feasible when this reaction was performed on a 10 mmol scale.
基金financial support from the National Natural Science Foundation of China(22125104 and 21831007)the Natural Science Foundation of Jiangsu Province(BK20210916)+1 种基金the High Education Natural Science Foundation of Jiangsu Province(No.21KJB150009)Undergraduate Students Project of Jiangsu Province(No.202110320019Z).
文摘A new class of m-hydroxybenzyl alcohols has been designed as competent three-carbon building blocks and achieved their applica-tion in 2-indolylmethanol-involved regioselective(3+3)cycloadditions under the catalysis of Br?nsted acids.By this appoach,a series of indole-fused six-membered cycloadducts have been synthesized in overall good yields(up to 98%)with excellent regioselectivity(all>95:5 rr),thus affording a powerful method for the construction of indole-fused six-membered rings.Moreover,a catalytic asymmetric version of this(3+3)cycloaddition has been preliminarily investigated,which revealed the potential of the reaction for constructing chiral indole-fused six-membered rings in an enantioselective manner.This work not only has accomplished the first design of m-hydroxybenzyl alcohols as competent reactants,but also represents the first application of m-hydroxybenzyl alcohols as three-carbon building blocks in cycloadditions.In addition,this work provides a good example for regioselective and C3-nucleophilic(3+3)cycloadditions of 2-indolylmethanols,which will substantially enrich the chemistry of 2-indolylmethanols.
基金the National Natural Science Foundation of China(Nos.21931002,22071098,22101115,and 22101123)the Shenzhen Science and Technology Innovation Committee(Nos.JCYJ20200109140812302 and JCYJ20210324105013035)the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)。
文摘Comprehensive Summary Metallacyclopentadienes play a vital role in transition-metal mediated and catalyzed cycloaddition reactions of alkynes.Though versatile reactions of metallacyclopentadienes with alkynes have been disclosed,[2+1]cycloadditions of metallacyclopentadienes and alkynes have never been discovered.In present work,we report the formal[2+1]cycloadditions of a metallacyclopentadiene unit with a broad scope of commercial alkynes,providing a facile strategy to construct tetracyclic conjugated compounds.The deuterated experiment indicates a metal vinylidene intermediate has been involved in[2+1]cycloaddition.Moreover,the electrophilic substitution reaction of the tetracyclic conjugated compound with the aid of density functional theory(DFT)calculated Fukui functions is investigated.
基金supported by the National Natural Science Foundation of China(22125104,21831007)the Natural Science Foundation of Jiangsu Province(BK20210916)the High Education Natural Science Foundation of Jiangsu Province(21KJB150009)。
文摘Chiral seven-membered ring systems such as seven-membered carbocycles and heterocycles are widely found in natural products and pharmaceuticals.Therefore,the catalytic enantioselective construction of such frameworks has evoked considerable interest in the field of chemistry.Among the various approaches,organocatalytic asymmetric(4+3)cycloadditions are highly effective for the enantioselective construction of seven-membered rings.Over the past two decades,substantial efforts have been devoted to this field and chemists have developed various organocatalytic asymmetric(4+3)cycloadditions.This review summarizes the progress in organocatalytic asymmetric(4+3)cycloadditions from 2003 to early 2022 and provides insights into challenging issues faced in this research field,enabling the future development of this field.
文摘Subject Code:B02 With the support by the National Natural Science Foundation of China,a collaborative study by the research groups led by Prof.Chen Yingchun(陈应春)from Sichuan University and Dr.Ouyang Qin(欧阳勤)from the Third Military Medical University demonstrates switchable regioselective[6+2]。
基金This work is supported by the National Natural Science Foundation of China(Nos.21772038 and 21971062)The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for the assistance with the HRMS and NMR analysis.
文摘The[8+4]cycloaddition of indene-2-carbaldehydes with indole-2,3-quinodimethanes and pyrrolidone-3,4-dienes is described,affording indole and pyrrolidone annulated bicyclo[4.2.1]nonanes in a highly peri-,diastereo-,and enantioselective fashion in the presence of a secondary amine catalyst.This reaction,which proceeds through catalytically generated isobenzofulvenes,represents the first asymmetric version of high-order[8+4]cycloaddition.
基金the National Natural Science Foundation of China(21901072)the China Postdoctoral Science Foundation(2019T120310)Shanghai Sailing Program(18YF140560)。
文摘The development of novel synthons and efficient methods to synthesize chiral polycyclic indoles has been a hot topic in organic synthesis and medicinal chemistry owing to their broad applications in medicines,pesticides,and other functional molecules.Here,we disclosed novel indolyl substituted metal-allyl zwitterionic intermediates through the decarboxylation of conveniently available vinyl indoloxazolidones,which could be regarded as two types of dipolar species through the anionic delocalization.The palladium-π-allyl species tended to serve as an all-carbon 1,3-dipole in the asymmetric[3+2]cycloaddition with electrondeficient alkenes,which furnished polysubstituted cyclopenta[b]indoles with high regio-and stereoselectivities.Meanwhile,the iridium-π-allyl species was recognized as an aza-1,3-dipole in asymmetric[3+2]cycloaddition with in situ generated C1 ammonium enolates,affording pyrrolo[1,2-α]indoles with high diastereo-and enantioselectivities.In addition,the dipolar cycloadditions could be easily scaled-up and several synthetic transformations of the cycloadducts were demonstrated for the rapid synthesis of diverse chiral polycyclic indoles.
基金supported by the National Natural Science Foundation of China (22025107, 21722105)the National Youth Top-notch Talent Support Program of China+2 种基金the Key Science and Technology Innovation Team of Shaanxi Province (2019TD-007, 2019JLZ-02)Xi’an Key Laboratory of Functional Supramolecular Structure and Materialsthe FM&EM International Joint Laboratory of Northwest University。
文摘Understanding and controlling supramolecular template effect assembly via a photochemical reaction in different solid and solution phases is one of the main topics in photochemistry. Here, an interesting case of phase-mediated controllable intramolecular/intermolecular photochemical [2+2] cycloadditions assisted by supramolecular templates was demonstrated. Direct irradiation of the complexes in solution yields intramolecular photoproducts exclusively, whereas exposure of the solid powder sample under the same conditions yields intermolecular dinuclear species quantitatively. The nature of the phase and supramolecular interaction affects the geometrical arrangements of the metallacycles, leading to different cycloaddition products under photoirradiation. The crystal structures of different products were investigated by single-crystal X-ray diffraction, nuclear magnetic resonance(NMR) spectrometry, and electrospray ionization mass spectrometry(ESI-MS).
基金supported by the National Natural Science Foundation of China(Nos.21302174,21672193 and 21272218)China Post-doctoral Science Foundation(No.2017M622362)+1 种基金Ministry of Industry and Information Technology of the People's Republic of China(No.Z135060009002)Key Research Projects of Universities in Henan Province(No.20A150040)。
文摘A cascade carbonylative ring expansion and [2+2]/[4+2] cycloaddition of strained 1-iminylphosphirane complexes with aryl allenes were reported.The carbonylative ring expansion of 1-iminylphosphirane complexes provides an azaphosphacyclohexone complex intermediate with a C=P double bond.The following [2+2] or dearomatic [4+2] cycloaddition of this intermediate with allenes is modulated by the aryl substituents on the imino carbon.The regioselective [2+2] cycloaddition with 1,1-diarylallene provides an entry to bicyclo[4.2.0]octan-4-one skeletons featuring a four-membered phosphacyclobutane moiety.While dearomatic [4+2] cycloaddition was preferred with less aromatic naphthalene and yielded octahydrochrysene skeleton containing heteroatoms.
基金supported by the Research Grants Council General Research Fund (No. 17301314)
文摘Furans bearing epoxy enolsilane units via a tether that incorporates a nitrogen heteroatom,undergo intramolecular(4+3)cycloadditions to generate bis-heteroatomic polycyclic adducts having piperidine moieties in their frameworks.The cycloadducts,ultimately derived from furfural,a renewal chemical feedstock,are obtained with up to 4:1 dr and with ee retained from the epoxide.
基金the financial support for this investigation from the National Natural Science Foundation of China(Nos.21772151,22072111)the Fundamental Research Funds for Central Universities(No.WUT:2021IVA121).
文摘The first example of stereoconvergent 1,3-dipolar cycloaddition of nitrile oxides and nitrile imines with E/Z isomeric mixture of electron-deficient olefins is reported,delivering isoxazolines and pyrazolines bearing two vicinal stereogenic tertiary and trifluoromethylated quaternary carbon centers with perfect regioand diastereoselectivities.The possibility of concerted cycloaddition/epimerization sequence under basic condition to form the thermodynamically stable diastereomers is excluded through some control experiments and DFT calculations,and a stepwise mechanism is proposed.
基金from the National Natural Science Foundation of China(grant nos.22071209 and 22071206)the National Youth Talent Support Program,the Natural Science Foundation of Fujian Province of China(grant no.2017J06006)+1 种基金the Fundamental Research Funds for the Central Universities(grant no.20720190048)Basic Disciplines Training Program for Top-notch Students of the Ministry of Education.
文摘Regiodivergent asymmetric cycloadditions from the same set of starting materials offer interesting opportunities for rapid construction of optically active cyclic molecules with structural diversity.However,this remains a challenging task due to the difficulty of simultaneously controlling the regio-,diastereo-,and enantioselectivity in the ring formation processes.To address this long-standing problem.
基金supported by the National Natural Science Foundation of China(U1705254,21871225,and 21931002)the Fundamental Research Funds for the Central Universities(20720190042),and the Research Grants Council of Hong Kong(N_HKUST603/15).
文摘Three-membered unsaturated rings have been widely utilized in organic synthesis due to their inherent highly strained structures.Although much research has been applied to ring-expansion reactions of such strained ring systems,pathways other than[3+2]cycloadditions have rarely been observed in their reactions with alkynes,and to date,no[3+1]cycloadditions of isolated three-membered unsaturated rings with alkynes have been reported.Here we demonstrate an unprecedented[3+1]cycloaddition in which a fused metalla-azirine is used as a template to generate a series of planar CCCCX-type(X=N,O,S)pentadentate carbolong complexes 3–6.A series of substituted alkynes was tested for further exploration of the scope and mechanism for the[3+1]cycloaddition reactions.Complexes 3–6 represent rare examples of planar pentadentate complexes that assemble fourπ-conjugated fused rings by one bridgehead atom.These novel complexes are thermally stable in air and absorb ultraviolet,visible,and near-infrared light,and thus are potentially applicable in photoelectric devices and pharmaceuticals.
基金financial support from the National Natural Science Foundation of China(22078274,21903066)。
文摘Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture and conversion of CO_(2)into value-added products,such as cyclic carbonates,is booming.While CO_(2)is an abundant,cheap,non-toxic,and readily accessible Cl feedstock,its thermodynamic stability necessitates the development of highly efficient catalysts that are able to promote chemical reactions under mild conditions.In this work,a novel mesoporous poly(ionic liquid)with dual active sites was synthesized through a facile method that involves co-polymerization,post-synthetic metalation,and supercritical CO_(2)drying.Due to a high density of nucleophilic and electrophilic sites,the as-prepared poly(ionic liquid),denoted as P2D-4BrBQA-Zn,offers excellent performance in a CO_(2)cycloaddition reaction using epichlorohydrin as the substrate(98.9%conversion and 96.9%selectivity).Moreover the reaction is carried out under mild,solvent-free,and additive-free conditions.Notably,P2D-4BrBQA-Zn also efficiently promotes the conversion of various other epoxide substrates into cyclic carbonates.Overall,the catalyst is found to have excellent substrate compatibility,stability,and recyclability.
文摘The synthesis of new indoloannulated thiopyranethiones is reported. The key-step is a rhodium-catalyzed [2 + 2 + 2]-cycloaddition of alkynyl-ynamides with carbon disulfide to close the pyrrole and the thiopyranethione rings simultaneously. A violet idolothiopyrane thione or a mixture of the violet and a red isomer result from [RhCl(C<sub>8</sub>H<sub>14</sub>)<sub>2</sub>]<sub>2</sub>/3BINAP catalyzed cycloadditions, the regiochemistry is controlled by the substitution pattern on the alkynyl-ynamide.
基金This work was supported by the National Science Fund for Excellent Young Scholars(21922813)and Key Research Program of Frontier Sciences of CAS(QYZDB-SSWSLH022)+2 种基金National Key Projects for Fundamental Research and Development of China(2017YFB0603301)DNL Cooperation Fund,CAS(DNL180202)and Youth Innovation Promotion Association of CAS(2017066).The authors sincerely appreciate Prof.Suojiang Zhang(IPE,CAS)for his careful academic guidance and great support.
文摘The cycloaddition of CO2 with epoxides catalyzed by ionic liquids(ILs)has been a widely ongoing studied hot topic over the years.Recent experimental research has shown that the protic ionic liquids(PILs)behave stronger hydrogen proton donating ability than aprotic ionic liquids(APILs),and can effectively catalyze the cycloaddition of CO2.Unfortunately,the mechanistic explanation remains primarily unraveled.Herein,a detailed simulation study on the cycloaddition reaction catalyzed by PIL([HDBU][Mim])in comparison with APIL([MeDBU][Mim])re-action catalysts was conducted,including the three-step route(ring-opening of PO(propylene oxide),insertion of CO2 and ring-closure of propylene carbonate(PC))and two-step route(simultaneously ring-opening of PO and addition of CO2,and then ring-closure of PC).Based on the activation energy barrier of the rate-determining step,PIL preferentially activates PO as the optimal route for the reaction with the energy barrier of 23.2 kcal mol-1,while that of APIL is 31.2 kcal mol-1.The role of[HDBU]+in the reaction was also explored and found that the direct formation of intermolecular hydrogen bond(H-bond)between[HDBU]+and the reactants(PO+CO2)was unfavorable for the reaction,while the cooperation with the anion[Mim]-to assist indirectly was more conducive.To fully consider the reaction microenvironment of ILs,ONIOM calculation was used to study the solvent effect.At last,the above conclusions were further verified by the analysis of intermediates with charge,non-covalent interaction(NCI),and atoms in molecules(AIM)methods.The computational findings show that ILs studied in this work have dual functions of catalyst and solvent,enabling a microscopic understanding of the ILs catalyst for CO2 utilization as well as providing guidance for the rational design of more efficient ILs-based catalysts.
基金supported by the National Key Projects for Fundamental R&D Program of China(2016YFB0600902)the NFSC of Tianjin(16JCZDJC36700 and 14JCQNJC03000)
文摘A double active center system, namely Salen-Cu(Ⅱ)@MIL-101(Cr), was successfully synthesized via the"ship in a bottle" approach, which acted as a bifunctional material for both capture and conversion of CO_2 in a single process. For the first time, Salen-Cu(Ⅱ)@MIL-101(Cr) catalyst was developed for the synthesis of propylene carbonate from CO_2 and propylene oxide under room temperature and ambient pressure with a yield of 87.8% over 60 h. Furthermore, the reaction mechanism was also discussed.
基金This work was supported by the NNSFC (No.29672004).
文摘Addition reaction of Grignard’s reagent to 5-methoxy-2(5H)-furanone 1 was accomplished, which provided a new possible route for synthesizing β-alkyl-γ-alkyloxy-γ-butyrolactone. A novel concise method of preparing fused heterocyclic compounds was offered by 1,3-dipolar cycloaddition reaction of silyl nitronates to 1.
基金financial support from the Program for New Century Excellent Talents in University(NCET-040270)。
文摘Two kinds of bi-functional transition metal doped mesoporous materials(Fe-HMS and Fe-MCM-41) are prepared using one-step hydrothermal method and then treated with hydrochloric acid ethanol solution.The N2 adsorption and HRTEM results show that both of Fe-HMS and Fe-MCM-41 possess mesoporous structure. The UV–vis results suggest that the Fe species are mainly located within the framework. The basicity of as-prepared samples was studied by temperature programmed desorption using CO2 as probe molecule(CO2-TPD). The catalytic performance of Fe-HMS and Fe-MCM-41 in CO2 cycloaddition largely depends on the amount of the accessible basic sites. The acid–base active sites, framework Fe and PDDA species cooperatively catalyze the CO2 cycloaddition for the production of cyclic carbonates under the condition without any co-catalyst. The conversion of epichlorohydrin(ECH) is 97.4% and the selectivity of chloropropene carbonate is 92.9% under optimal conditions. The approximate rate constant of cycloaddition reaction of CO2 with ECH under optimum reaction temperature is calculated. It is worth noting that the Fe-HMS material shows superior reusability than Fe-MCM-41. In addition, this work provides a facile way on the synthesis of bi-functional acid–base heterogeneous catalyst with outstanding catalytic performance for the fixation of CO2.