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
Phosphorus stereocenter,a ubiquitous central chiral element,plays a crucial role in pharmaceuticals,materials science and asymmetric catalysis.As such,stereoselective construction of phosphorus stereocenters has becom...Phosphorus stereocenter,a ubiquitous central chiral element,plays a crucial role in pharmaceuticals,materials science and asymmetric catalysis.As such,stereoselective construction of phosphorus stereocenters has become important in the field of organic synthesis.Herein we report a general and modular method for the construction of P-stereogenic centers via palladium/chiral norbornene cooperative catalysis-enabled desymmetrization/kinetic resolution process.It is a two-component annulation reaction that involves widely available aryl iodides and prochiral or racemic phosphinamides as the reactants.A wide variety of substrates bearing an assortment of functional groups(50 examples)are compatible with this method.Other features include a distinct enantiodiscrimination mechanism,excellent stereoselectivities,and scalability.The obtained chiral P-stereogenic products bear a common C–Br bond,which can be elaborated for the synthesis of new P-stereogenic compounds with diverse structural features.In addition,preliminary studies uncover the promising chiroptical properties of these P-stereogenic cyclic phosphinamides.Density functional theory calculations are performed to reveal that the noncovalent hydrogen bonding interaction is the origin of enantiodiscrimination during the desymmetrization process.展开更多
Many sensitizers have not only photodynamic effects,but also sonodynamic effects.Therefore,the combination of sonodynamic therapy(SDT)and photodynamic therapy(PDT)using sensitizers for sonophotodynamic therapy(SPDT)pr...Many sensitizers have not only photodynamic effects,but also sonodynamic effects.Therefore,the combination of sonodynamic therapy(SDT)and photodynamic therapy(PDT)using sensitizers for sonophotodynamic therapy(SPDT)provides alternative opportunities for clinical cancer therapy.Although significant advances have been made in synthesizing new sensitizers for SPDT,few of them are successfully applied in clinical settings.The anti-tumor effects of the sensitizers are restricted by the lack of tumor-targeting specificity,incapability in deep intratumoral delivery,and the deteriorating tumor microenvironment.The application of nanotechnology-based drug delivery systems(NDDSs)can solve the above shortcomings,thereby improving the SPDT efficacy.This review summarizes various sensitizers as sono/photosensitizers that can be further used in SPDT,and describes different strategies for enhancing tumor treatment by NDDSs,such as overcoming biological barriers,improving tumor-targeted delivery and intratumoral delivery,providing stimuli-responsive controlled-release characteristics,stimulating anti-tumor immunity,increasing oxygen supply,employing different therapeutic modalities,and combining diagnosis and treatment.The challenges and prospects for further development of intelligent sensitizers and translational NDDSs for SPDT are also discussed.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.
基金the National Key Research and Development Program of China(grant no.2022YFA1503703)the National Natural Science Foundation of China(grant no.22325106)the Fundamental Research Funds for the Central Universities(grant no.2042024kf1014),and Wuhan University for financial support.
文摘Phosphorus stereocenter,a ubiquitous central chiral element,plays a crucial role in pharmaceuticals,materials science and asymmetric catalysis.As such,stereoselective construction of phosphorus stereocenters has become important in the field of organic synthesis.Herein we report a general and modular method for the construction of P-stereogenic centers via palladium/chiral norbornene cooperative catalysis-enabled desymmetrization/kinetic resolution process.It is a two-component annulation reaction that involves widely available aryl iodides and prochiral or racemic phosphinamides as the reactants.A wide variety of substrates bearing an assortment of functional groups(50 examples)are compatible with this method.Other features include a distinct enantiodiscrimination mechanism,excellent stereoselectivities,and scalability.The obtained chiral P-stereogenic products bear a common C–Br bond,which can be elaborated for the synthesis of new P-stereogenic compounds with diverse structural features.In addition,preliminary studies uncover the promising chiroptical properties of these P-stereogenic cyclic phosphinamides.Density functional theory calculations are performed to reveal that the noncovalent hydrogen bonding interaction is the origin of enantiodiscrimination during the desymmetrization process.
基金supported by the National Natural Science Foundation of China(81871481 and 81571802)the Fujian Provincial Youth Top-notch Talent Support program(China)National Key R&D Program of China(2020YFA0210800)
文摘Many sensitizers have not only photodynamic effects,but also sonodynamic effects.Therefore,the combination of sonodynamic therapy(SDT)and photodynamic therapy(PDT)using sensitizers for sonophotodynamic therapy(SPDT)provides alternative opportunities for clinical cancer therapy.Although significant advances have been made in synthesizing new sensitizers for SPDT,few of them are successfully applied in clinical settings.The anti-tumor effects of the sensitizers are restricted by the lack of tumor-targeting specificity,incapability in deep intratumoral delivery,and the deteriorating tumor microenvironment.The application of nanotechnology-based drug delivery systems(NDDSs)can solve the above shortcomings,thereby improving the SPDT efficacy.This review summarizes various sensitizers as sono/photosensitizers that can be further used in SPDT,and describes different strategies for enhancing tumor treatment by NDDSs,such as overcoming biological barriers,improving tumor-targeted delivery and intratumoral delivery,providing stimuli-responsive controlled-release characteristics,stimulating anti-tumor immunity,increasing oxygen supply,employing different therapeutic modalities,and combining diagnosis and treatment.The challenges and prospects for further development of intelligent sensitizers and translational NDDSs for SPDT are also discussed.
