A mild and practical protocol for selectively time-dependent dehydrogenative C–C coupling,as well as tandem couplingcyclization reaction between indoles or/and other heteroaromatics via electrochemically oxidative pr...A mild and practical protocol for selectively time-dependent dehydrogenative C–C coupling,as well as tandem couplingcyclization reaction between indoles or/and other heteroaromatics via electrochemically oxidative process has been demonstrated.The reaction runs under noble catalyst,external oxidant and inert gas free condition,allowing tunable access to a wide variety of synthetically useful symmetrical or nonsymmetrical heteroarene with aggregation-induced emission(AIE),and polycyclic 3-D indole derivatives with aggregation-caused quenching(ACQ)fluorescence properties.Finally,preliminary mechanistic study indicated that tunable generation of indole cation under various electrolysis potential via regulating Nprotecting group was the key to achieve cross-coupling between indoles and other heteroaromatics.展开更多
Electro-oxidation of phenylamine derivatives（1a and 1b） have been studied in the presence of pyrazolidine-3,5-dione（3） as a nucleophile in phosphate buffer solution mixed with ethanol,using voltammetric and spectr...Electro-oxidation of phenylamine derivatives（1a and 1b） have been studied in the presence of pyrazolidine-3,5-dione（3） as a nucleophile in phosphate buffer solution mixed with ethanol,using voltammetric and spectroscopic techniques.The obtained results indicated that the oxidized form of phenylamines（2a and 2b） participate in Michael addition type reactions with pyrazolidine-3,5-dione（3） and via ECECCCCC mechanisms convert to the corresponding new polycyclic indoles（12a and 12b）.In the present study,new polycyclic indole derivatives were synthesized with good yields and high purity using a facile,one-pot and environmentally friendly electrochemical method,without any chemical catalysts,toxic solvents and hard conditions.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
Tetrahydro-y-carbolines(THyCs)constitute one of the most important subtypes of indole alkaloids.In addition to being substructures of natural products,these structural motifs and moieties can often be found in pharmac...Tetrahydro-y-carbolines(THyCs)constitute one of the most important subtypes of indole alkaloids.In addition to being substructures of natural products,these structural motifs and moieties can often be found in pharmaceuticals due to their diverse bioactivities such as antiviral,antibacterial,antifungal,antiparasitic,antitumor,anti-inflammatory,and neuropharmacological activities.Beyond the pharmacological and biological aspects of these scaffolds,they have considerable synthetic applications for the construction of further bioactive compounds,too.The aim of this review is to summarize recent developments in the synthesis of this compound class.展开更多
基金supported by Guangdong Basic and Applied Basic Research Foundation (2019A1515011743)the Pearl River talent program of Guangdong Province (Youth Top-Notch Talent,2017GC010302)Jinan University
文摘A mild and practical protocol for selectively time-dependent dehydrogenative C–C coupling,as well as tandem couplingcyclization reaction between indoles or/and other heteroaromatics via electrochemically oxidative process has been demonstrated.The reaction runs under noble catalyst,external oxidant and inert gas free condition,allowing tunable access to a wide variety of synthetically useful symmetrical or nonsymmetrical heteroarene with aggregation-induced emission(AIE),and polycyclic 3-D indole derivatives with aggregation-caused quenching(ACQ)fluorescence properties.Finally,preliminary mechanistic study indicated that tunable generation of indole cation under various electrolysis potential via regulating Nprotecting group was the key to achieve cross-coupling between indoles and other heteroaromatics.
基金Semnan University Research Council for financial support of this work
文摘Electro-oxidation of phenylamine derivatives（1a and 1b） have been studied in the presence of pyrazolidine-3,5-dione（3） as a nucleophile in phosphate buffer solution mixed with ethanol,using voltammetric and spectroscopic techniques.The obtained results indicated that the oxidized form of phenylamines（2a and 2b） participate in Michael addition type reactions with pyrazolidine-3,5-dione（3） and via ECECCCCC mechanisms convert to the corresponding new polycyclic indoles（12a and 12b）.In the present study,new polycyclic indole derivatives were synthesized with good yields and high purity using a facile,one-pot and environmentally friendly electrochemical method,without any chemical catalysts,toxic solvents and hard conditions.
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financial support from the National Natural Science Foundation of China(No.21761132021)financial support from the National Research,Development and Innovation Office of Hungary(No.NKFIH/OTKA K 142266).
文摘Tetrahydro-y-carbolines(THyCs)constitute one of the most important subtypes of indole alkaloids.In addition to being substructures of natural products,these structural motifs and moieties can often be found in pharmaceuticals due to their diverse bioactivities such as antiviral,antibacterial,antifungal,antiparasitic,antitumor,anti-inflammatory,and neuropharmacological activities.Beyond the pharmacological and biological aspects of these scaffolds,they have considerable synthetic applications for the construction of further bioactive compounds,too.The aim of this review is to summarize recent developments in the synthesis of this compound class.
