Comprehensive Summary.Herein, an intermolecular palladium(II)-catalyzed regioselective [4+2] benzannulation reaction capable of converting 2-pyridones into quinolinones was developed using electron-deficient alkenes a...Comprehensive Summary.Herein, an intermolecular palladium(II)-catalyzed regioselective [4+2] benzannulation reaction capable of converting 2-pyridones into quinolinones was developed using electron-deficient alkenes as two-carbon units. An examination of the reaction mechanism indicated that the extension from 2-pyridone to quinolinone was likely facilitated through a series of sequential C—H activation reactions or 6π electrocyclization, culminating in dehydrogenative aromatization. This method of diversity-oriented synthesis of quinolinone derivatives is characterized by a broad substrate scope, atom economy, and excellent chemical selectivity. In addition, these quinolinone derivatives exhibit fluorescent absorption within the visible-light spectrum, which makes them suitable candidates for the development of innovative fluorescent probes.展开更多
Herein,we report an asymmetric two-component alkenyl Catellani reaction for the construction of C—N axial chirality through a palladium/chiral norbornene cooperative catalysis and an axial-to-axial chirality transfer...Herein,we report an asymmetric two-component alkenyl Catellani reaction for the construction of C—N axial chirality through a palladium/chiral norbornene cooperative catalysis and an axial-to-axial chirality transfer process.Various partially aromatic iodinated 2-pyridones,quinolones,coumarin and uracil substrates react with 2,6-disubstituted aryl bromides with a tethered amide group,to afford a wide variety of polycyclic C—N atropisomers(38 examples,up to 97%e.e.).The obtained C—N axial chirality originates from the preformed transient C—C axial chirality with high fidelity.The synthetic utility of this chemistry is demonstrated by facile prepa-ration of complex quinoline and pyridine based C—N atropisomers through a N-deprotection and aromatization sequence.In addi-tion,a remote axial-to-central diastereoinduction process dictated by C—N axial chirality is observed with excellent diastereocontrol.展开更多
基金the Natural Science Foundation of Anhui University of Chinese Medicine(2021rczd003 and 2022AH050440)the Cooperation Project of Fuyang Municipal Government and Fuyang Normal University(No.SXHZ202002)+1 种基金the Natural Science Foundation of Fuyang Normal University(FYKFKT24001)the National Natural Science Foundation of China(Grant No.22301074)for financial support.
文摘Comprehensive Summary.Herein, an intermolecular palladium(II)-catalyzed regioselective [4+2] benzannulation reaction capable of converting 2-pyridones into quinolinones was developed using electron-deficient alkenes as two-carbon units. An examination of the reaction mechanism indicated that the extension from 2-pyridone to quinolinone was likely facilitated through a series of sequential C—H activation reactions or 6π electrocyclization, culminating in dehydrogenative aromatization. This method of diversity-oriented synthesis of quinolinone derivatives is characterized by a broad substrate scope, atom economy, and excellent chemical selectivity. In addition, these quinolinone derivatives exhibit fluorescent absorption within the visible-light spectrum, which makes them suitable candidates for the development of innovative fluorescent probes.
文摘Herein,we report an asymmetric two-component alkenyl Catellani reaction for the construction of C—N axial chirality through a palladium/chiral norbornene cooperative catalysis and an axial-to-axial chirality transfer process.Various partially aromatic iodinated 2-pyridones,quinolones,coumarin and uracil substrates react with 2,6-disubstituted aryl bromides with a tethered amide group,to afford a wide variety of polycyclic C—N atropisomers(38 examples,up to 97%e.e.).The obtained C—N axial chirality originates from the preformed transient C—C axial chirality with high fidelity.The synthetic utility of this chemistry is demonstrated by facile prepa-ration of complex quinoline and pyridine based C—N atropisomers through a N-deprotection and aromatization sequence.In addi-tion,a remote axial-to-central diastereoinduction process dictated by C—N axial chirality is observed with excellent diastereocontrol.
