A palladium-catalyzed cascade cyclization of allenylethylene carbonates with 1,3-indandiones was developed, providing biologically interesting tetracyclic dihydrocyclopentaindenofuranone derivatives having three conti...A palladium-catalyzed cascade cyclization of allenylethylene carbonates with 1,3-indandiones was developed, providing biologically interesting tetracyclic dihydrocyclopentaindenofuranone derivatives having three contiguous quaternary carbon centers in moderate to high yields with excellent diastereoselectivities. In this reaction, the allene moiety was fully fused into the cyclopentene ring.展开更多
The cycloaddition and annulation reactions offer a powerful method toward various important substituted 3,4-dihydro-2H-pyran architectures.Nevertheless,the transformation for preparing fused-polycyclic ones still rema...The cycloaddition and annulation reactions offer a powerful method toward various important substituted 3,4-dihydro-2H-pyran architectures.Nevertheless,the transformation for preparing fused-polycyclic ones still remains challenging yet highly desirable until now.Herein,we report a novel formal[3+3]cascade cyclization reaction to provide lactam-fused 4-fluoroalkylated 3,4-dihydropyran skeletons bearing three contiguous tertiary carbon centers via copper catalysis.Of note,these annulations proceeded in an exclusively diastereoselective manner through successive inert C(sp^(2))-Cl and C(sp^(3))-H functionalization,which exhibited highly site-selectivity and stereoselectivity.Additionally,evaluations on biological activities of the obtained products revealed that several products display inhibitory activity against Siha and H1975 cancer cell lines.展开更多
Dihydropyran(DHP)compounds are not only found in natural products and bioactive molecules,but also serve as important precursors in organic synthesis.Nonetheless,traditional methods for the construction of such compou...Dihydropyran(DHP)compounds are not only found in natural products and bioactive molecules,but also serve as important precursors in organic synthesis.Nonetheless,traditional methods for the construction of such compounds are usually limited to disubstituted DHPs.To address this synthetic challenge,reported here is an efficient electrochemical strategy toward the selenated and trifluoromethylated DHP compounds.The reaction proceeded smoothly under mild electrolysis conditions.The broad substrate scope(>50 examples)and scalable synthesis demonstrated the complexity-building potential of the strategy.Initial mechanistic studies reveal that cyclization may involve a radical process.This protocol may promote the further development of diversified synthesis of multi-substituted dihydropyran.展开更多
A simple and efficient cascade Michael/cyclization reaction of 3-aminoindolin-2-ones with enones/enals was identified for the synthesis of potentially biologically active 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles], ...A simple and efficient cascade Michael/cyclization reaction of 3-aminoindolin-2-ones with enones/enals was identified for the synthesis of potentially biologically active 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles], using DBU as an efficient catalyst and ethylene glycol as an environmentally benign solvent. More diverse 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles] analog libraries were prepared in good yields（up to 97%）. The structure of 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles] was confirmed by mass spectrometry analysis, NMR analysis and single crystal X-ray diffraction. The main advantages of this method include the availability of starting materials, simple experimental operation, short reaction time,as well as high yields observed.展开更多
An efficient method has been developed for the cascade synthesis of azo[1,2-a]indolones from azoles and2-fluoroaldehydes based on an iron-catalyzed SNAr and a direct acylation reaction.A number of azo[1,2-a]indolones ...An efficient method has been developed for the cascade synthesis of azo[1,2-a]indolones from azoles and2-fluoroaldehydes based on an iron-catalyzed SNAr and a direct acylation reaction.A number of azo[1,2-a]indolones containing different azole rings and substituents were obtained in good yields.展开更多
A highly efficient,transition-metal-and light-free approach to polyheterocycles via regioselective cascade radical cyclization is developed.The redox-neutral protocol has a broad substrate scope with good functional g...A highly efficient,transition-metal-and light-free approach to polyheterocycles via regioselective cascade radical cyclization is developed.The redox-neutral protocol has a broad substrate scope with good functional group tolerance and probably undergoes a SET process,which is initiated by catalytic amounts of quinone in combination with 2.0 equiv.of Cs_(2)CO_(3).展开更多
An alkyl radical initiated cyclization/tandem reaction of alkyl bromides and alkyl electrophiles by using potassium metabisulphite(K_(2)S_(2)O_(5))as a connector is developed for the synthesis of various lactam-substi...An alkyl radical initiated cyclization/tandem reaction of alkyl bromides and alkyl electrophiles by using potassium metabisulphite(K_(2)S_(2)O_(5))as a connector is developed for the synthesis of various lactam-substituted alkyl sulfones.Notably,this process does not require a metal catalyst or metal powder reductant,highlighting its environmentally friendly features.The reaction demonstrates outstanding substrate adaptability and a high tolerance towards diverse functional groups.Furthermore,the biologically active molecules and commercially available drugs with a late-stage modification are also highly compatible with this transformation.Mechanistic studies revealed that the reaction proceeds through a single-step process involving intramolecular radical cyclization,"SO_(2)"insertion,and external alkyl incorporation.展开更多
The ruthenium-catalyzed intermolecular cascade cyclization of aromatic acids with aromatic aldehydes, which involves the direct insertion of C–H bond into a polar C=O bond and the successive intramolecular nucleophil...The ruthenium-catalyzed intermolecular cascade cyclization of aromatic acids with aromatic aldehydes, which involves the direct insertion of C–H bond into a polar C=O bond and the successive intramolecular nucleophilic substitution, was developed for the synthesis of 3-substituted phthalides in good to excellent yields. This one-pot procedure characterizes in a short reaction time, the cheaper Ru(II) as a catalyst, readily available acids and aldehydes as starting materials, and water as the only theoretical by-product.These merits make the protocol an efficient and cost-effective route for the synthesis of 3-substituted phthalides.展开更多
Functionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules.Ynones are good regional selectivity radical acceptors in orga...Functionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules.Ynones are good regional selectivity radical acceptors in organic synthesis,and many of bio-relevant cyclic compounds could be easily obtained by direct radical cyclization reaction.Here,we report a photocatalytic cascade radical addition of biaryl ynones,for the divergent synthesis of privileged carbon cycles.Additionally,further transformation of the multi-functional group product into a variety of other derivatives demonstrates the synthetic value of this developed method.展开更多
Herein,it is reported that the aryl radicals derived from aryl thianthrenium salts are used as coupling partner in the arylation reactions of isocyanides,simultaneously as initiators for the formation of alkyl and pho...Herein,it is reported that the aryl radicals derived from aryl thianthrenium salts are used as coupling partner in the arylation reactions of isocyanides,simultaneously as initiators for the formation of alkyl and phosphoryl radicals from ethers and diarylphosphine oxides.This cascade cyclization reaction leads to diverse arylated,alkylated and phosphorylated heteroaromatic compounds.Notably,this transformation can be achieved without the aid of metals or photocatalysts,exhibiting a wide substrate applicability and operational simplicity.Mechanistic studies suggest the involvement of radical processes and electron donor-acceptor(EDA)complexes in this transformation.展开更多
An efficient photochemical radical sulfonyl cyclization of designed dienes to medium-sized benzo[b]azocines and benzo[b]azonines was developed.This chemoselective method provides new highly functionalized eight-and ni...An efficient photochemical radical sulfonyl cyclization of designed dienes to medium-sized benzo[b]azocines and benzo[b]azonines was developed.This chemoselective method provides new highly functionalized eight-and nine-membered N-heterocycles.Radical inhibition experiments,light on/off experiments,and apparent quantum efficiency calculations were used to clarify the radical mechanism.Density functional theory calculations enabled rationalization of the rate-determining step and observed chemoselectivity.Large-scale synthesis and derivatizations via epoxidation and convenient N-Ts deprotection showed the potential utility of this strategy.This photochemical method for synthesizing sulfonylbenzo[b]azocines and sulfonylbenzo[b]azonines with insertion of sulfur dioxide provides new sustainable routes for the synthesis of valuable medium-sized Nheterocycles.展开更多
基金supported by the Natural Science Foundation of China(Nos.21871293 and 22071264)。
文摘A palladium-catalyzed cascade cyclization of allenylethylene carbonates with 1,3-indandiones was developed, providing biologically interesting tetracyclic dihydrocyclopentaindenofuranone derivatives having three contiguous quaternary carbon centers in moderate to high yields with excellent diastereoselectivities. In this reaction, the allene moiety was fully fused into the cyclopentene ring.
基金the Talents Program of Guangdong Province(2023QN10Y314)Guangdong Basic and Applied Basic Research Foundation(2024A151501212,2023A1515012657)+3 种基金Zhanjiang Ocean Young Talent Innovation Project(2023E0002)The Research Fund of Talents Program of Guangdong Medical University(4RS23002d4SG24248G)The Cultivating Research Fund of Guangdong Medical University(2XJ24006)。
文摘The cycloaddition and annulation reactions offer a powerful method toward various important substituted 3,4-dihydro-2H-pyran architectures.Nevertheless,the transformation for preparing fused-polycyclic ones still remains challenging yet highly desirable until now.Herein,we report a novel formal[3+3]cascade cyclization reaction to provide lactam-fused 4-fluoroalkylated 3,4-dihydropyran skeletons bearing three contiguous tertiary carbon centers via copper catalysis.Of note,these annulations proceeded in an exclusively diastereoselective manner through successive inert C(sp^(2))-Cl and C(sp^(3))-H functionalization,which exhibited highly site-selectivity and stereoselectivity.Additionally,evaluations on biological activities of the obtained products revealed that several products display inhibitory activity against Siha and H1975 cancer cell lines.
基金supported by the National Key R&D Program of China(2022YFA1505100,2021YFA1500100)the National Natural Science Foundation of China(22031008)+1 种基金the Fundamental Research Funds for the Central Universities(2042022rc0030,2042023kf0108,2042023kf1002)the Science Foundation of Wuhan(2020010601012192)。
文摘Dihydropyran(DHP)compounds are not only found in natural products and bioactive molecules,but also serve as important precursors in organic synthesis.Nonetheless,traditional methods for the construction of such compounds are usually limited to disubstituted DHPs.To address this synthetic challenge,reported here is an efficient electrochemical strategy toward the selenated and trifluoromethylated DHP compounds.The reaction proceeded smoothly under mild electrolysis conditions.The broad substrate scope(>50 examples)and scalable synthesis demonstrated the complexity-building potential of the strategy.Initial mechanistic studies reveal that cyclization may involve a radical process.This protocol may promote the further development of diversified synthesis of multi-substituted dihydropyran.
基金Financial support for this work by the National Natural Science Foundation of China(No.81202403)West China HospitalChengdu Science and Technology Department Translational Medicine Innovation Foundation(No.ZH13039)
文摘A simple and efficient cascade Michael/cyclization reaction of 3-aminoindolin-2-ones with enones/enals was identified for the synthesis of potentially biologically active 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles], using DBU as an efficient catalyst and ethylene glycol as an environmentally benign solvent. More diverse 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles] analog libraries were prepared in good yields（up to 97%）. The structure of 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles] was confirmed by mass spectrometry analysis, NMR analysis and single crystal X-ray diffraction. The main advantages of this method include the availability of starting materials, simple experimental operation, short reaction time,as well as high yields observed.
基金financially supported by the Natural Science Foundation of China(Nos.21302135 and 21272169)Taizhou Science & Technology program(No.111ZD02)
文摘An efficient method has been developed for the cascade synthesis of azo[1,2-a]indolones from azoles and2-fluoroaldehydes based on an iron-catalyzed SNAr and a direct acylation reaction.A number of azo[1,2-a]indolones containing different azole rings and substituents were obtained in good yields.
基金the financial support from the National Natural Science Foundation of China(No.21472159)the Natural Science Foundation of Guangdong Province(No.2018A0303130021)+2 种基金the Guangdong Basic and Applied Basic Research Funds(No.2021A1515012023)Fundamental Research Funds for the Central Universities(Nos.21620318 and 2019QNGG22)the Open Fund of Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications(No.2020B121201005).
文摘A highly efficient,transition-metal-and light-free approach to polyheterocycles via regioselective cascade radical cyclization is developed.The redox-neutral protocol has a broad substrate scope with good functional group tolerance and probably undergoes a SET process,which is initiated by catalytic amounts of quinone in combination with 2.0 equiv.of Cs_(2)CO_(3).
基金the Scientific Research Fund of Hunan Provincial Education Department(21B0262 and 22B1094)the Natural Science Foundation of Hunan Province(2022JJ40857)the Hunan Provincial Innovation Foundation For Postgraduate(CX20230757)forfinancial support.
文摘An alkyl radical initiated cyclization/tandem reaction of alkyl bromides and alkyl electrophiles by using potassium metabisulphite(K_(2)S_(2)O_(5))as a connector is developed for the synthesis of various lactam-substituted alkyl sulfones.Notably,this process does not require a metal catalyst or metal powder reductant,highlighting its environmentally friendly features.The reaction demonstrates outstanding substrate adaptability and a high tolerance towards diverse functional groups.Furthermore,the biologically active molecules and commercially available drugs with a late-stage modification are also highly compatible with this transformation.Mechanistic studies revealed that the reaction proceeds through a single-step process involving intramolecular radical cyclization,"SO_(2)"insertion,and external alkyl incorporation.
基金supported by the National Science Foundation of China (21572122, 21376146)Shaanxi Innovative Team of Key Science and Technology (2013KCT-17)the Fundamental Research Funds for the Central Universities (GK201703019, GK 201601005)
文摘The ruthenium-catalyzed intermolecular cascade cyclization of aromatic acids with aromatic aldehydes, which involves the direct insertion of C–H bond into a polar C=O bond and the successive intramolecular nucleophilic substitution, was developed for the synthesis of 3-substituted phthalides in good to excellent yields. This one-pot procedure characterizes in a short reaction time, the cheaper Ru(II) as a catalyst, readily available acids and aldehydes as starting materials, and water as the only theoretical by-product.These merits make the protocol an efficient and cost-effective route for the synthesis of 3-substituted phthalides.
基金the Natural Science Foundation of Zhejiang Province(LY22B020001)the Zhejiang Public Welfare Public Research Program(LGC22B010001)the National Natural Science Foundation of China(32201238)is greatly acknowledged.
文摘Functionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules.Ynones are good regional selectivity radical acceptors in organic synthesis,and many of bio-relevant cyclic compounds could be easily obtained by direct radical cyclization reaction.Here,we report a photocatalytic cascade radical addition of biaryl ynones,for the divergent synthesis of privileged carbon cycles.Additionally,further transformation of the multi-functional group product into a variety of other derivatives demonstrates the synthetic value of this developed method.
基金supported by the National Youth Talent Support Program,Guangdong Basic and Applied Basic Research Foundation(2024B1515040027)Guangzhou Science and Technology Projects(2024A04J6248).
文摘Herein,it is reported that the aryl radicals derived from aryl thianthrenium salts are used as coupling partner in the arylation reactions of isocyanides,simultaneously as initiators for the formation of alkyl and phosphoryl radicals from ethers and diarylphosphine oxides.This cascade cyclization reaction leads to diverse arylated,alkylated and phosphorylated heteroaromatic compounds.Notably,this transformation can be achieved without the aid of metals or photocatalysts,exhibiting a wide substrate applicability and operational simplicity.Mechanistic studies suggest the involvement of radical processes and electron donor-acceptor(EDA)complexes in this transformation.
基金supported by the National Natural Science Foundation of China(21801007)Qingchuang Technology Support Program of University in Shandong Province(2021KJ066)funding from the STU Scientific Research Foundation for Talents(NTF20022)。
文摘An efficient photochemical radical sulfonyl cyclization of designed dienes to medium-sized benzo[b]azocines and benzo[b]azonines was developed.This chemoselective method provides new highly functionalized eight-and nine-membered N-heterocycles.Radical inhibition experiments,light on/off experiments,and apparent quantum efficiency calculations were used to clarify the radical mechanism.Density functional theory calculations enabled rationalization of the rate-determining step and observed chemoselectivity.Large-scale synthesis and derivatizations via epoxidation and convenient N-Ts deprotection showed the potential utility of this strategy.This photochemical method for synthesizing sulfonylbenzo[b]azocines and sulfonylbenzo[b]azonines with insertion of sulfur dioxide provides new sustainable routes for the synthesis of valuable medium-sized Nheterocycles.
