The C-H and C-C bonds are abundant in organic compounds,yet generally inert in chemical transformations.Therefore,direct functionalization of inert chemical bonds remains challenging.The fluorine-containing compounds ...The C-H and C-C bonds are abundant in organic compounds,yet generally inert in chemical transformations.Therefore,direct functionalization of inert chemical bonds remains challenging.The fluorine-containing compounds are of special interest for their uses in medicinal chemistry.Direct fluorination of C-H and C-C bonds undoubtedly represents one of the most ideal and attractive approaches to incorporate fluorine atom into complex molecules.Herein,we summarize the recent advances in radical-mediated C-H and C-C bond fluorination.Three types of transformations are discussed:(1)direct C-H abstraction/fluorination of alkanes;(2)decarboxylative fluorination of alkyl carboxylic acids;(3)ring-opening fluorination.展开更多
Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides has been successfully achieved.It was found that both the catalytic amount of sodium dithionite (Na2S2O4) and the stoi...Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides has been successfully achieved.It was found that both the catalytic amount of sodium dithionite (Na2S2O4) and the stoichiometric amount of triethylborane (Et3B)/air can efficiently initiate the current free-radical atom transfer reaction.展开更多
The reactions between gatifloxacin(GFX) and various one-electron oxidants,such as ˙OH,N3˙,Br2˙ˉ,and SO4˙ˉ,have been studied by pulse radiolysis techniques.The GFX radical anion formed in the reaction of GFX with...The reactions between gatifloxacin(GFX) and various one-electron oxidants,such as ˙OH,N3˙,Br2˙ˉ,and SO4˙ˉ,have been studied by pulse radiolysis techniques.The GFX radical anion formed in the reaction of GFX with eaqˉ could either be protonated or deprotonated,and the absorption of GFX radical anion was located at 390 nm.The transient species produced by the reaction of GFX with ˙OH radical shows a broad band in the 380?600 nm region with a shoulder,while the oxidation by N3˙,SO4˙ˉ,and Br2˙ˉ results in an absorption band with λmax = 370 nm.At neutral condition(pH 7),the rate constants of GFX reacting with ˙OH,N3˙,Br2˙ˉ,SO4˙ˉ and eaqˉ are estimated to be 1.0 × 1010,3.1 × 109,2.8 × 109,3.0 × 109,and 1.8 × 1010 dm3 mol?1 s?1,respectively.From the pH dependence on the formation of electron adducts and on the rate constant of GFX with eaqˉ,the pKa of GFX radical anion is estimated to be 5.5 and 9.3.展开更多
基金Project Supported by the National Nature Science Foundation of Chinathe Center for Computational Science,Hefei Institutes of Physical Sciences(0330405002)
基金supported by Soochow University,the National Natural Science Foundation of China(21402134)the Natural Science Foundation of Jiangsu Province(BK20140306)the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘The C-H and C-C bonds are abundant in organic compounds,yet generally inert in chemical transformations.Therefore,direct functionalization of inert chemical bonds remains challenging.The fluorine-containing compounds are of special interest for their uses in medicinal chemistry.Direct fluorination of C-H and C-C bonds undoubtedly represents one of the most ideal and attractive approaches to incorporate fluorine atom into complex molecules.Herein,we summarize the recent advances in radical-mediated C-H and C-C bond fluorination.Three types of transformations are discussed:(1)direct C-H abstraction/fluorination of alkanes;(2)decarboxylative fluorination of alkyl carboxylic acids;(3)ring-opening fluorination.
基金financially supported by the National Natural Science Foundation of China (20825209, 20832008, 20772144)the Chinese Academy of Sciences (Hundreds-Talent Program and Knowledge Innovation Program)
文摘Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides has been successfully achieved.It was found that both the catalytic amount of sodium dithionite (Na2S2O4) and the stoichiometric amount of triethylborane (Et3B)/air can efficiently initiate the current free-radical atom transfer reaction.
基金supported by the National Natural Science Foundation of China (21173252)
文摘The reactions between gatifloxacin(GFX) and various one-electron oxidants,such as ˙OH,N3˙,Br2˙ˉ,and SO4˙ˉ,have been studied by pulse radiolysis techniques.The GFX radical anion formed in the reaction of GFX with eaqˉ could either be protonated or deprotonated,and the absorption of GFX radical anion was located at 390 nm.The transient species produced by the reaction of GFX with ˙OH radical shows a broad band in the 380?600 nm region with a shoulder,while the oxidation by N3˙,SO4˙ˉ,and Br2˙ˉ results in an absorption band with λmax = 370 nm.At neutral condition(pH 7),the rate constants of GFX reacting with ˙OH,N3˙,Br2˙ˉ,SO4˙ˉ and eaqˉ are estimated to be 1.0 × 1010,3.1 × 109,2.8 × 109,3.0 × 109,and 1.8 × 1010 dm3 mol?1 s?1,respectively.From the pH dependence on the formation of electron adducts and on the rate constant of GFX with eaqˉ,the pKa of GFX radical anion is estimated to be 5.5 and 9.3.
