The direct preparation of a kind of fluorinating reagent 1[F-TEDA-N(SO_(2)Ph)_(2)]was realized in high yield via the complexation of N-fluorobenzenesulfonimide(NFSI)with 1-(chloromethyl)-1,4-diazabicyclo[2.2.2]octan-1...The direct preparation of a kind of fluorinating reagent 1[F-TEDA-N(SO_(2)Ph)_(2)]was realized in high yield via the complexation of N-fluorobenzenesulfonimide(NFSI)with 1-(chloromethyl)-1,4-diazabicyclo[2.2.2]octan-1-ium N',N'-bis-(benzenesulfonylimide)salt.In its fluorination to oxindoles,the fluorinating products 6 were afforded in moderate to high yields.展开更多
Construction of C-F bonds is a direct and efficient method for introducing fluorine into pharmaceuticals,agrochemicals,and materials.Strategies such as nucleophilic,electrophilic,radical,and transition-metal catalyzed...Construction of C-F bonds is a direct and efficient method for introducing fluorine into pharmaceuticals,agrochemicals,and materials.Strategies such as nucleophilic,electrophilic,radical,and transition-metal catalyzed fluorination have been developed to meet the demand of diverse C-F bond formation.Among them,radical fluorination has been witnessed with substantial advancement in a recent decade.Herein,we reviewed methods for formation of C-F bonds with carbon-centered radicals as key intermediates,especially in recent five years.We introduce in the paper with different fluorinating reagents,strategies for radical generation,and application in late-stage functionalization and synthesis of PET tracers.We also indicate the current limitations and propose the direction of the field for the future development.展开更多
N-Fluorobenzenesulfonimide (NFSI) is one of the most popular fluorine-containing reagents for fluorination, imidation, sulfonylation, and oxidation reactions. Consequently, a variety of NFSI derivatives were designed ...N-Fluorobenzenesulfonimide (NFSI) is one of the most popular fluorine-containing reagents for fluorination, imidation, sulfonylation, and oxidation reactions. Consequently, a variety of NFSI derivatives were designed and synthesized to modify the reactivity and/or selectivity of the parent reagent. However, the hazardous F_(2) was inevitably required for the synthesis of NFSI derivatives. Herein, we disclosed a practical synthesis of various NFSI derivatives without F_(2) in common organic chemistry laboratories. This synthetic protocol started from NFSI through pyridine-promoted desulfonylation for formation of N-fluoroarenesulfonamide (ArSO_(2)NHF) and followed by condensation with arenesulfonyl chlorides. The reduction potentials and fluorinating reactivities of these NFSI derivatives demonstrated that NFSI derivatives bearing the electron-withdrawing groups on benzene ring had the higher oxidizing and fluorinating abilities than NFSI.展开更多
基金the National Natural Science Foundation of China(No.21372077)for their financial supports.
文摘The direct preparation of a kind of fluorinating reagent 1[F-TEDA-N(SO_(2)Ph)_(2)]was realized in high yield via the complexation of N-fluorobenzenesulfonimide(NFSI)with 1-(chloromethyl)-1,4-diazabicyclo[2.2.2]octan-1-ium N',N'-bis-(benzenesulfonylimide)salt.In its fluorination to oxindoles,the fluorinating products 6 were afforded in moderate to high yields.
基金the National Natural Science Foundation of China(22301224)Wuhan Science and Technology Project(2023020201020273),and Wuhan University for financial support.We thank Prof.Wen-Bo Liu(Wuhan University)for proof reading.
文摘Construction of C-F bonds is a direct and efficient method for introducing fluorine into pharmaceuticals,agrochemicals,and materials.Strategies such as nucleophilic,electrophilic,radical,and transition-metal catalyzed fluorination have been developed to meet the demand of diverse C-F bond formation.Among them,radical fluorination has been witnessed with substantial advancement in a recent decade.Herein,we reviewed methods for formation of C-F bonds with carbon-centered radicals as key intermediates,especially in recent five years.We introduce in the paper with different fluorinating reagents,strategies for radical generation,and application in late-stage functionalization and synthesis of PET tracers.We also indicate the current limitations and propose the direction of the field for the future development.
基金The National Natural Science Foundation of China(21991211)the National Key Research and Development Program of China(2021YFF0701700)are greatly acknowledged for funding this work.
文摘N-Fluorobenzenesulfonimide (NFSI) is one of the most popular fluorine-containing reagents for fluorination, imidation, sulfonylation, and oxidation reactions. Consequently, a variety of NFSI derivatives were designed and synthesized to modify the reactivity and/or selectivity of the parent reagent. However, the hazardous F_(2) was inevitably required for the synthesis of NFSI derivatives. Herein, we disclosed a practical synthesis of various NFSI derivatives without F_(2) in common organic chemistry laboratories. This synthetic protocol started from NFSI through pyridine-promoted desulfonylation for formation of N-fluoroarenesulfonamide (ArSO_(2)NHF) and followed by condensation with arenesulfonyl chlorides. The reduction potentials and fluorinating reactivities of these NFSI derivatives demonstrated that NFSI derivatives bearing the electron-withdrawing groups on benzene ring had the higher oxidizing and fluorinating abilities than NFSI.
