Described herein is an efficient protocol for the regioselective introduction of a vinyl trifluoromethylthioether to remote unactivated C(sp3)–H bonds.The cascade process involves the vinyl radical-mediated 1,5-hydro...Described herein is an efficient protocol for the regioselective introduction of a vinyl trifluoromethylthioether to remote unactivated C(sp3)–H bonds.The cascade process involves the vinyl radical-mediated 1,5-hydrogen atom transfer(HAT)and remote vinyl migration.During the transformation,inert C–H and C–C bonds are consecutively cleaved under mild conditions.The reaction features good functional group tolerance,broad substrate scope,and high regio-/stereo-selectivity.展开更多
A promoter-free Friedel-Crafts trifluoromethylthiolation of electron-rich arenes and heteroarenes with N-trifluoromethylthiosaccharin 5 using 2,2,2-trifluoroethanol(TFE) as the solvent was described.The reactions were...A promoter-free Friedel-Crafts trifluoromethylthiolation of electron-rich arenes and heteroarenes with N-trifluoromethylthiosaccharin 5 using 2,2,2-trifluoroethanol(TFE) as the solvent was described.The reactions were conducted at 40℃and a variety of common functional groups were compatible.展开更多
An organocatalytic asymmetric trifluoromethylthiolation of 3-aryl or 3-alkyloxindoles employing a trifluoromethyl-substituted thioperoxide as the electrophilic trifluoromethylthiolating reagent was described.Reactions...An organocatalytic asymmetric trifluoromethylthiolation of 3-aryl or 3-alkyloxindoles employing a trifluoromethyl-substituted thioperoxide as the electrophilic trifluoromethylthiolating reagent was described.Reactions occurred in good to excellent enantioselectivities to generate oxindoles with a SCF_(3)-substituted quaternary chiral center.展开更多
A novel photocatalyzed trifluoromethylthio-trifluoromethylation of alkenes has been developed,using CF_(3)SO_(2)Na as both CF_(3) and SCF_(3) source.This photocatalyzed dual-oxidative strategy,which combines two paral...A novel photocatalyzed trifluoromethylthio-trifluoromethylation of alkenes has been developed,using CF_(3)SO_(2)Na as both CF_(3) and SCF_(3) source.This photocatalyzed dual-oxidative strategy,which combines two parallel oxidative events,provides a facile method to synthesize a series of vicinal trifluoromethylthio-trifluoromethylated compounds.This reaction is operationally simple,proceeds under mild conditions and exhibits exceptional substrate generality and functional group compatibility.展开更多
Rational design of new bioisosteres through introduction of high-value functional groups to bicyclo[1.1.1]pentane(BCP)is of particular use for drug discovery.Disclosed herein is the first access to valuable fluoroalky...Rational design of new bioisosteres through introduction of high-value functional groups to bicyclo[1.1.1]pentane(BCP)is of particular use for drug discovery.Disclosed herein is the first access to valuable fluoroalkylthio(seleno)-functionalized BCPs.A range of SCF3,SCF2H,SCFH2,SeCF3,SeC4F9,and SeC8F17 groups are readily incorporated to BCPs under mild conditions.Concomitant installation of a sulfone provides a platform for incorporation of the BCP motif to bioactive molecules.This practical protocol features novel BCP scaffolds,broad substrate scope,excellent atom-economy,simple operation,and gramscale preparation.展开更多
A new method for the preparation of fluoroalkylthioethers including trifluoromethylthioether and difluoromethylthioether by iridium(Ⅰ)-catalyzed deoxgenation of fluoroalkylsulfoxides with dimethyl diazomalonate was d...A new method for the preparation of fluoroalkylthioethers including trifluoromethylthioether and difluoromethylthioether by iridium(Ⅰ)-catalyzed deoxgenation of fluoroalkylsulfoxides with dimethyl diazomalonate was developed.In the reaction system,dimethyl diazomalonate was used as reducing reagent and the corresponding fluoroalkylthioethers were produced through oxygen atom transfer from fluoroalkylsulfoxides to diazomalonate.The protocol featuring effective oxygen atom transfer,mild reaction conditions and good functional groups tolerance offers an alternative strategy for the synthesis of fluoroalkylthioethers.展开更多
基金supported by Soochow University,the National Natural Science Foundation of China(21722205)the Project of Scientific and Technologic Infrastructure of Suzhou(SZS201708)the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Described herein is an efficient protocol for the regioselective introduction of a vinyl trifluoromethylthioether to remote unactivated C(sp3)–H bonds.The cascade process involves the vinyl radical-mediated 1,5-hydrogen atom transfer(HAT)and remote vinyl migration.During the transformation,inert C–H and C–C bonds are consecutively cleaved under mild conditions.The reaction features good functional group tolerance,broad substrate scope,and high regio-/stereo-selectivity.
基金the financial support from the National Natural Science Foundation of China (Nos.21625206, 21632009,21572258,21421002)the Natural Science Foundation of Shanghai (No.17ZR1447100)the Science and Technology Commission of Shanghai Municipality (No.14DZ2261000)
文摘A promoter-free Friedel-Crafts trifluoromethylthiolation of electron-rich arenes and heteroarenes with N-trifluoromethylthiosaccharin 5 using 2,2,2-trifluoroethanol(TFE) as the solvent was described.The reactions were conducted at 40℃and a variety of common functional groups were compatible.
基金The authors gratefully acknowledge the financial support from National Basic Research Program of China(2012CB821600)the Key Program of Natural Science Foundation of China(21032006)National Natural Science Foundation of China(21172245/21172244/21372247)and 100-talent program of SIOC.
文摘An organocatalytic asymmetric trifluoromethylthiolation of 3-aryl or 3-alkyloxindoles employing a trifluoromethyl-substituted thioperoxide as the electrophilic trifluoromethylthiolating reagent was described.Reactions occurred in good to excellent enantioselectivities to generate oxindoles with a SCF_(3)-substituted quaternary chiral center.
基金This research was made possible as a result of a generous grant from XYZ Foundation(grant no.123567).
文摘A novel photocatalyzed trifluoromethylthio-trifluoromethylation of alkenes has been developed,using CF_(3)SO_(2)Na as both CF_(3) and SCF_(3) source.This photocatalyzed dual-oxidative strategy,which combines two parallel oxidative events,provides a facile method to synthesize a series of vicinal trifluoromethylthio-trifluoromethylated compounds.This reaction is operationally simple,proceeds under mild conditions and exhibits exceptional substrate generality and functional group compatibility.
基金supported by the National Natural Science Foundation of China(21722205,21971173)the Project of Scientific and Technologic Infrastructure of Suzhou(SZS201905)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘Rational design of new bioisosteres through introduction of high-value functional groups to bicyclo[1.1.1]pentane(BCP)is of particular use for drug discovery.Disclosed herein is the first access to valuable fluoroalkylthio(seleno)-functionalized BCPs.A range of SCF3,SCF2H,SCFH2,SeCF3,SeC4F9,and SeC8F17 groups are readily incorporated to BCPs under mild conditions.Concomitant installation of a sulfone provides a platform for incorporation of the BCP motif to bioactive molecules.This practical protocol features novel BCP scaffolds,broad substrate scope,excellent atom-economy,simple operation,and gramscale preparation.
基金supported by the Natural Science Foundation of Shanghai(No.20ZR1471600)the Science and Technology Commission of Shanghai Municipality(No.19DZ2271100)the Open Research Fund Program of CAS Key Laboratory of Energy Regulation Materials(No.ORFP2020–06)。
文摘A new method for the preparation of fluoroalkylthioethers including trifluoromethylthioether and difluoromethylthioether by iridium(Ⅰ)-catalyzed deoxgenation of fluoroalkylsulfoxides with dimethyl diazomalonate was developed.In the reaction system,dimethyl diazomalonate was used as reducing reagent and the corresponding fluoroalkylthioethers were produced through oxygen atom transfer from fluoroalkylsulfoxides to diazomalonate.The protocol featuring effective oxygen atom transfer,mild reaction conditions and good functional groups tolerance offers an alternative strategy for the synthesis of fluoroalkylthioethers.
