Chloroalkanes are important building blocks in the synthesis,but their use in redox chemistry is limited by their negative reduction potentials.Electrosynthesis can precisely control the reaction energy just by adjust...Chloroalkanes are important building blocks in the synthesis,but their use in redox chemistry is limited by their negative reduction potentials.Electrosynthesis can precisely control the reaction energy just by adjusting the current or voltage to achieve the selectivity of regulation.In this study,the consecutively paired electrolyticmediated controllable radical cross-coupling of thiophenols with dichloromethane was developed to deliver the dithioacetals,sulfides,and sulfoxides in the absence of electrochemical mediator conditions.It features broad substrate scope,simple operation,gram-scale synthesis,and is eco-friendly.Mechanistic studies reveal that this electrochemical reaction is radical-induced cross-coupling of thiophenols with dichloromethane.展开更多
This paper presents a series of first- and second-generation click-modified coumarin-based fluorescent probes for thiols. These molecules demonstrate high turn-on fluorescent response and good selectivity towards arom...This paper presents a series of first- and second-generation click-modified coumarin-based fluorescent probes for thiols. These molecules demonstrate high turn-on fluorescent response and good selectivity towards aromatic thiols over other relevant reac- tive sulfur species, reactive oxygen species and common nucleophiles. Moreover, probe la can detect thiols in the reduced rabbit plasma sample. Therefore, this approach provides a particularly impressive tool for detecting thiol in biological systems.展开更多
Late-stage peptide modification showcases a huge potential for the construction of peptide libraries,and the investigation of structure-activity relationships.Herein we report a dimethyl sulfoxide/visible light comedi...Late-stage peptide modification showcases a huge potential for the construction of peptide libraries,and the investigation of structure-activity relationships.Herein we report a dimethyl sulfoxide/visible light comediated chemoselective modification of tryptophan residue by forging the C-S structure using thiophenols irradiated with blue light-emitting diodes at room temperature.This method shows excellent chemoselectivity toward the C-2 position of the tryptophan residue and good compatibility with diverse thiophenol derivatives bearing various functional groups.Both protected oligopeptides and unmasked bioactive peptides smoothly underwent site-selective modification,furnishing the corresponding products.Above all,this study provides a new competent toolkit for late-stage peptide modification,labelling,and peptide-drug conjugation and provides a clue for protein bioconjugation.展开更多
基金This work is supported by the National Natural Science Foundation of China(No.21902083)the Natural Science Foundation of Shandong Province(No.ZR2020QB130)This work is also supported by the Talent Program Foundation of Qufu Normal University(Nos.6132 and 6125).
文摘Chloroalkanes are important building blocks in the synthesis,but their use in redox chemistry is limited by their negative reduction potentials.Electrosynthesis can precisely control the reaction energy just by adjusting the current or voltage to achieve the selectivity of regulation.In this study,the consecutively paired electrolyticmediated controllable radical cross-coupling of thiophenols with dichloromethane was developed to deliver the dithioacetals,sulfides,and sulfoxides in the absence of electrochemical mediator conditions.It features broad substrate scope,simple operation,gram-scale synthesis,and is eco-friendly.Mechanistic studies reveal that this electrochemical reaction is radical-induced cross-coupling of thiophenols with dichloromethane.
基金financed by grants from Shandong Natural Science Foundation (JQ201019)Independent Innovation Foundation of Shandong University,IIFSDU (2010JQ005)
文摘This paper presents a series of first- and second-generation click-modified coumarin-based fluorescent probes for thiols. These molecules demonstrate high turn-on fluorescent response and good selectivity towards aromatic thiols over other relevant reac- tive sulfur species, reactive oxygen species and common nucleophiles. Moreover, probe la can detect thiols in the reduced rabbit plasma sample. Therefore, this approach provides a particularly impressive tool for detecting thiol in biological systems.
基金the CAMS Innovation Fund for Medical Sciences(CIFMS)(grant nos.2019-I2M-5-074,2021-I2M-1-026,2021-I2M-3-001,and 2022-I2M-2-002)the National Natural Science Foundation of China(grant nos.81773564,82173678 and 22307052)+2 种基金the Program for Chang-Jiang Scholars and Innovative Research Team in University(grant no.IRT_15R27)the fellowship of China Postdoctoral Science Foundation(grant no.2021M701533)the Gansu Science and Technology Program(grant nos.23JRRA1103,22JR5RA502,and 21JR7RA449).
文摘Late-stage peptide modification showcases a huge potential for the construction of peptide libraries,and the investigation of structure-activity relationships.Herein we report a dimethyl sulfoxide/visible light comediated chemoselective modification of tryptophan residue by forging the C-S structure using thiophenols irradiated with blue light-emitting diodes at room temperature.This method shows excellent chemoselectivity toward the C-2 position of the tryptophan residue and good compatibility with diverse thiophenol derivatives bearing various functional groups.Both protected oligopeptides and unmasked bioactive peptides smoothly underwent site-selective modification,furnishing the corresponding products.Above all,this study provides a new competent toolkit for late-stage peptide modification,labelling,and peptide-drug conjugation and provides a clue for protein bioconjugation.
