A novel and efficient copper-catalyzed decarboxylative alkynylselenation of indoles with Se powder and propiolic acids has been developed.The outstanding advantages of this protocol not only nicely avoid the use of pr...A novel and efficient copper-catalyzed decarboxylative alkynylselenation of indoles with Se powder and propiolic acids has been developed.The outstanding advantages of this protocol not only nicely avoid the use of prefabricated arylselenation reagent and address the facile over-selention issues,but also enrich the chemistry of selenium powder.Importantly,this reaction could be extended to pyrrole,and the practical utility of this transformation has been demonstrated in gram-scale synthesis and late-stage indolylselenation of Clofibrate-derived propiolic acid.展开更多
The conversion of inexpensive,available C1 feedstock of carbon dioxide(CO_(2))into value-added fine chemicals via homogeneous or heterogeneous catalysis has attracted great recent interest.Coinagemetal-based(Cu,Ag,and...The conversion of inexpensive,available C1 feedstock of carbon dioxide(CO_(2))into value-added fine chemicals via homogeneous or heterogeneous catalysis has attracted great recent interest.Coinagemetal-based(Cu,Ag,and Au)catalysis has emerged as a synthetic strategy for a wide range of organic chemical reactions in past decades.In coinage-metal-catalyzed carboxylation,CO_(2)is adopted as a carboxylation reagent,while coinage-metal salts,complexes,and nanoparticles(NPs)serve as a Lewis acid catalyst to activate unsaturated chemicals,particularly alkynes.This mini-review focuses on the recent advances of coinage-metal-catalyzed carboxylation of terminal alkynes with CO_(2).Other respects,such as the role of bases,the influence of trace water,and solvent effects are also highlighted.展开更多
Transition-metal catalyzed cross-coupling is one of the basic strategies for the C-C bond formation.However,it is difficult to achieve satisfactory results when terminal alkynes with electron-withdrawing group such as...Transition-metal catalyzed cross-coupling is one of the basic strategies for the C-C bond formation.However,it is difficult to achieve satisfactory results when terminal alkynes with electron-withdrawing group such as propiolate esters are used.The reason behind this might be the easy polymerization of this type of alkynes in the presence of base.A tetrahydroxydiboron and copper sulfate co-promoted cross-coupling/cyclization of propiolate esters and o-iodobenzoic acid for the facile and efficient construction of phthalides is described.Preliminary mechanism study indicates that tetrahydroxydiboron can inhibit the polymerization of propiolate esters and increase the reaction rate.This method is characterized by high regio-and stereoselectivities,mild reaction conditions,short reaction time,broad substrate scope,and excellent functional group compatibility.展开更多
The addition of 2,4-dihydroxyaceto(and benzo)phenone to propiolic ester is catalyzed by triphenylphosphine or tert-butyl isocyanide to form O-vinyl aryl derivatives in fairly good yields.
A novel, convenient and efficient approach to the synthesis of pyrrole and imidazole derivatives via the reaction between primary amines, alkyl propiolates or isothiocyanate and oxalyl chloride is described. The metho...A novel, convenient and efficient approach to the synthesis of pyrrole and imidazole derivatives via the reaction between primary amines, alkyl propiolates or isothiocyanate and oxalyl chloride is described. The method offers several advantages including high yields of products and performing reaction under solvent-free conditions.展开更多
The addition of α-keto amides as a NH-acid to alkyl propiolates and dialkyl acetylenedicarboxylates in the presence of a catalytic amount of triphenylphosphine gives the corresponding substituted alkyl acrylates.
Stable derivatives of pyrroles were prepared using multicomponent reactions of dialkyl acetylenedicarboxylate, primary amine and propiolate in the presence of N-methylimidazole in water at room temperature in good yie...Stable derivatives of pyrroles were prepared using multicomponent reactions of dialkyl acetylenedicarboxylate, primary amine and propiolate in the presence of N-methylimidazole in water at room temperature in good yields.展开更多
A three-component condensation was applied for the preparation of cyclopentadiene derivatives through the reaction of primary amines,alkyl propiolate and dialkyl acetylenedicarboxylate in the presence of catalytic amo...A three-component condensation was applied for the preparation of cyclopentadiene derivatives through the reaction of primary amines,alkyl propiolate and dialkyl acetylenedicarboxylate in the presence of catalytic amount of ZnO-nanorods（Zn-NR） under solvent-free conditions at 50 ℃.The method has proved to be synthetically green,simple,and effective with high atom economy and yield.The catalyst also revealed significant reusability.Moreover,the antioxidant activity and free radical scavenging capacity of the newly synthesized derivatives 4a,4b,4c,and 4d was screened using free radical scavenging 2,2-diphenyl-1-picrylhydrazyl（DPPH） and ferric reducing antioxidant power（FRAP）assays and compared with hydroxytoluene（BHT） and tert-butylhydroquinone（TBHQ）.These compounds do not exhibit good DPPH radical scavenging,but they have a desirable FRAP.展开更多
The synthesis and structures of two novel zwitterionic ruthenium triazolato complexes are reported. The treatment of the ruthenium azido complex [Ru]-N3 (1, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with an ex...The synthesis and structures of two novel zwitterionic ruthenium triazolato complexes are reported. The treatment of the ruthenium azido complex [Ru]-N3 (1, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with an excess of ethyl propiolate in CHCl3 or CH2Cl2 under ambient conditions for 15 days results in the formation of a mixture of the Z- and E-forms of N(1)-bound ruthenium 3-ethylacryl-4-carboxylate-3H-1,2,3-triazolato complexes [Ru]N3(CH=CHCO2Et)C2H(CO2) (Z-3) and (E-3) in a ratio of ca. 5:2. The structures of E-3 and Z-3 were confirmed by single-crystal X-ray diffraction analysis and fully characterized by 1H, 31P, 13C NMR and IR spectroscopy, mass spectrometry, and elemental analysis. The negatively charged carboxylate moieties of the zwitterionic ruthenium triazolato complexes Z-3 and Z-3 are highly nucleophilic and reactive toward a variety of electrophiles, making Z-3 and Z-3 potential starting materials for the development of biologically active 1,2,3-triazole derivatives.展开更多
CO_2 incorporation into C-H bonds is an important and interesting topic. Herein a sequential protocol for C(sp)-H carboxylation by employing a metal-free C-H activation/catalytic silylation reaction in conjunction wit...CO_2 incorporation into C-H bonds is an important and interesting topic. Herein a sequential protocol for C(sp)-H carboxylation by employing a metal-free C-H activation/catalytic silylation reaction in conjunction with KO^tBu-mediated carboxylation with CO_2 was established, in which KO^t Bu catalyzes silylation of terminal alkynes to form alkynylsilanes at low temperature, and simultaneously mediates carboxylation of the alkynesilanes with atmospheric CO_2. Importantly, the carboxylation further promotes the silylation, which makes the whole reaction proceed very rapidly. Moreover, this methodology is simple and scalable, which is characterized by short reaction time, wide substrate scope, excellent functional-group tolerance and mild reaction conditions,affording a range of corresponding propiolic acid products in excellent yields in most cases. In addition, it also allows for a convenient ^(13)C-labeling through the use of ^(13)CO_2.展开更多
Regioseletive 1,3-dipolar polycycloadditions of 4,4'-isopropylidenediphenyl dipropiolate (1) and tetraphenylethene (TPE)-containing diazides (2) are carried out in polar solvents such as DMF/toluene at a moderate ...Regioseletive 1,3-dipolar polycycloadditions of 4,4'-isopropylidenediphenyl dipropiolate (1) and tetraphenylethene (TPE)-containing diazides (2) are carried out in polar solvents such as DMF/toluene at a moderate temperature of 100℃ for 6 h,producing poly(aroxycarbonyltriazole)s (PACTs) P3 with high molecular weights (Mw up to 23900) and regioregularities (F1,4 up to ～90%) in high yields (up to ～99%).These metal-free click polymerizations can propagate smoothly in an open atmosphere without protection from oxygen and moisture.The obtained polymers are soluble in common organic solvents and thermally stable at temperatures up to 375℃.Thanks to their contained TPE moieties,the PACTs show aggregation-induced emission and can serve as fluorescent chemosensors for superamplified detection of explosives.展开更多
The one-pot sequential reaction of arylamines, methyl propiolate and 2-aryl-3-nitrochromenes without any catalyst in refluxing ethanol afforded the polysubstituted 3-（3-nitro-2-phenylchroman-4-yl）-3-arylaminoacrylat...The one-pot sequential reaction of arylamines, methyl propiolate and 2-aryl-3-nitrochromenes without any catalyst in refluxing ethanol afforded the polysubstituted 3-（3-nitro-2-phenylchroman-4-yl）-3-arylaminoacrylates in good yields and with high diastereoselectivity. Reaction mechanism was believed involving the initial formation of β-enamino ester and sequential Michael addition.展开更多
A simple, environmental-friendly, and practical method for the synthesis of benzodiazepine derivatives through a reaction of substituted o-phenylenediamines with alkyl propiolates has been developed. The reactions gen...A simple, environmental-friendly, and practical method for the synthesis of benzodiazepine derivatives through a reaction of substituted o-phenylenediamines with alkyl propiolates has been developed. The reactions generated the 1,5-benzodiazepines in good to excellent yields in the presence of catalytic amount of In（OTf）3 under sol- vent-free reaction conditions.展开更多
基金Financial support from the National Natural Science Foundation of China(Nos.81803484,21602158)Zhejiang Provincial Natural Science Foundation(No.LY19B020011)Public Welfare Science and Technology Project of Wenzhou(Nos.Y20190132,Y20180233)are greatly appreciated.
文摘A novel and efficient copper-catalyzed decarboxylative alkynylselenation of indoles with Se powder and propiolic acids has been developed.The outstanding advantages of this protocol not only nicely avoid the use of prefabricated arylselenation reagent and address the facile over-selention issues,but also enrich the chemistry of selenium powder.Importantly,this reaction could be extended to pyrrole,and the practical utility of this transformation has been demonstrated in gram-scale synthesis and late-stage indolylselenation of Clofibrate-derived propiolic acid.
文摘The conversion of inexpensive,available C1 feedstock of carbon dioxide(CO_(2))into value-added fine chemicals via homogeneous or heterogeneous catalysis has attracted great recent interest.Coinagemetal-based(Cu,Ag,and Au)catalysis has emerged as a synthetic strategy for a wide range of organic chemical reactions in past decades.In coinage-metal-catalyzed carboxylation,CO_(2)is adopted as a carboxylation reagent,while coinage-metal salts,complexes,and nanoparticles(NPs)serve as a Lewis acid catalyst to activate unsaturated chemicals,particularly alkynes.This mini-review focuses on the recent advances of coinage-metal-catalyzed carboxylation of terminal alkynes with CO_(2).Other respects,such as the role of bases,the influence of trace water,and solvent effects are also highlighted.
文摘Transition-metal catalyzed cross-coupling is one of the basic strategies for the C-C bond formation.However,it is difficult to achieve satisfactory results when terminal alkynes with electron-withdrawing group such as propiolate esters are used.The reason behind this might be the easy polymerization of this type of alkynes in the presence of base.A tetrahydroxydiboron and copper sulfate co-promoted cross-coupling/cyclization of propiolate esters and o-iodobenzoic acid for the facile and efficient construction of phthalides is described.Preliminary mechanism study indicates that tetrahydroxydiboron can inhibit the polymerization of propiolate esters and increase the reaction rate.This method is characterized by high regio-and stereoselectivities,mild reaction conditions,short reaction time,broad substrate scope,and excellent functional group compatibility.
文摘The addition of 2,4-dihydroxyaceto(and benzo)phenone to propiolic ester is catalyzed by triphenylphosphine or tert-butyl isocyanide to form O-vinyl aryl derivatives in fairly good yields.
文摘A novel, convenient and efficient approach to the synthesis of pyrrole and imidazole derivatives via the reaction between primary amines, alkyl propiolates or isothiocyanate and oxalyl chloride is described. The method offers several advantages including high yields of products and performing reaction under solvent-free conditions.
文摘The addition of α-keto amides as a NH-acid to alkyl propiolates and dialkyl acetylenedicarboxylates in the presence of a catalytic amount of triphenylphosphine gives the corresponding substituted alkyl acrylates.
文摘Stable derivatives of pyrroles were prepared using multicomponent reactions of dialkyl acetylenedicarboxylate, primary amine and propiolate in the presence of N-methylimidazole in water at room temperature in good yields.
基金the support of the Research Council of Iran University of Science and Technology, Tehran, Iran
文摘A three-component condensation was applied for the preparation of cyclopentadiene derivatives through the reaction of primary amines,alkyl propiolate and dialkyl acetylenedicarboxylate in the presence of catalytic amount of ZnO-nanorods（Zn-NR） under solvent-free conditions at 50 ℃.The method has proved to be synthetically green,simple,and effective with high atom economy and yield.The catalyst also revealed significant reusability.Moreover,the antioxidant activity and free radical scavenging capacity of the newly synthesized derivatives 4a,4b,4c,and 4d was screened using free radical scavenging 2,2-diphenyl-1-picrylhydrazyl（DPPH） and ferric reducing antioxidant power（FRAP）assays and compared with hydroxytoluene（BHT） and tert-butylhydroquinone（TBHQ）.These compounds do not exhibit good DPPH radical scavenging,but they have a desirable FRAP.
文摘The synthesis and structures of two novel zwitterionic ruthenium triazolato complexes are reported. The treatment of the ruthenium azido complex [Ru]-N3 (1, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with an excess of ethyl propiolate in CHCl3 or CH2Cl2 under ambient conditions for 15 days results in the formation of a mixture of the Z- and E-forms of N(1)-bound ruthenium 3-ethylacryl-4-carboxylate-3H-1,2,3-triazolato complexes [Ru]N3(CH=CHCO2Et)C2H(CO2) (Z-3) and (E-3) in a ratio of ca. 5:2. The structures of E-3 and Z-3 were confirmed by single-crystal X-ray diffraction analysis and fully characterized by 1H, 31P, 13C NMR and IR spectroscopy, mass spectrometry, and elemental analysis. The negatively charged carboxylate moieties of the zwitterionic ruthenium triazolato complexes Z-3 and Z-3 are highly nucleophilic and reactive toward a variety of electrophiles, making Z-3 and Z-3 potential starting materials for the development of biologically active 1,2,3-triazole derivatives.
基金supported by the National Natural Science Foundation of China(21503239,21533011,21402208,21403252)
文摘CO_2 incorporation into C-H bonds is an important and interesting topic. Herein a sequential protocol for C(sp)-H carboxylation by employing a metal-free C-H activation/catalytic silylation reaction in conjunction with KO^tBu-mediated carboxylation with CO_2 was established, in which KO^t Bu catalyzes silylation of terminal alkynes to form alkynylsilanes at low temperature, and simultaneously mediates carboxylation of the alkynesilanes with atmospheric CO_2. Importantly, the carboxylation further promotes the silylation, which makes the whole reaction proceed very rapidly. Moreover, this methodology is simple and scalable, which is characterized by short reaction time, wide substrate scope, excellent functional-group tolerance and mild reaction conditions,affording a range of corresponding propiolic acid products in excellent yields in most cases. In addition, it also allows for a convenient ^(13)C-labeling through the use of ^(13)CO_2.
基金supported by the National Natural Science Foundation of China (20634020,50703033,20974098 and 20974028)the Ministry of Science and Technology of China (2009CB623605)+4 种基金the University Grants Committee of Hong Kong ( AoE/P-03/08)the Research Grants Council of Hong Kong (603509,601608 and 602707)the Innovation and Technology Fund of Hong Kong (ITS/168/09). A.J.Q. and B.Z.T acknowledge the supports from the Postdoctoral Research Foundation of China (20081461)the Fundamental Research Funds for the Central Universities (2010KYJD005)the CAO GuangBiao Foundation of Zhejiang University,respectively
文摘Regioseletive 1,3-dipolar polycycloadditions of 4,4'-isopropylidenediphenyl dipropiolate (1) and tetraphenylethene (TPE)-containing diazides (2) are carried out in polar solvents such as DMF/toluene at a moderate temperature of 100℃ for 6 h,producing poly(aroxycarbonyltriazole)s (PACTs) P3 with high molecular weights (Mw up to 23900) and regioregularities (F1,4 up to ～90%) in high yields (up to ～99%).These metal-free click polymerizations can propagate smoothly in an open atmosphere without protection from oxygen and moisture.The obtained polymers are soluble in common organic solvents and thermally stable at temperatures up to 375℃.Thanks to their contained TPE moieties,the PACTs show aggregation-induced emission and can serve as fluorescent chemosensors for superamplified detection of explosives.
基金This work was financially supported by the National Natural Science Foundation of China，the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘The one-pot sequential reaction of arylamines, methyl propiolate and 2-aryl-3-nitrochromenes without any catalyst in refluxing ethanol afforded the polysubstituted 3-（3-nitro-2-phenylchroman-4-yl）-3-arylaminoacrylates in good yields and with high diastereoselectivity. Reaction mechanism was believed involving the initial formation of β-enamino ester and sequential Michael addition.
基金Project supported bythe National Natural Science Foundation of China（Nol 20972057）.
文摘A simple, environmental-friendly, and practical method for the synthesis of benzodiazepine derivatives through a reaction of substituted o-phenylenediamines with alkyl propiolates has been developed. The reactions generated the 1,5-benzodiazepines in good to excellent yields in the presence of catalytic amount of In（OTf）3 under sol- vent-free reaction conditions.
