The divergent reductive cross-coupling with an ambident electrophile is rare.Previously,we demonstrated a nickel-catalyzed reductive 2-pyridination of aryl iodides with difluoromethyl 2-pyridyl sulfone(2-Py SO_(2)CF_(...The divergent reductive cross-coupling with an ambident electrophile is rare.Previously,we demonstrated a nickel-catalyzed reductive 2-pyridination of aryl iodides with difluoromethyl 2-pyridyl sulfone(2-Py SO_(2)CF_(2)H)via selective C(sp^(2))-S bond cleavage of the sulfone by using a phosphine ligand.In this communication,we report a novel nickel-catalyzed reductive coupling of aryl iodides and 2-Py SO_(2)CF_(2)H reagent,which constitutes a new method for aromatic difluoromethylation.The use of a tridentate terpyridine ligand is pivotal for the selective C(sp^(3))-S bond cleavage of the sulfone.This method employs readily available nickel catalyst and 2-Py SO_(2)CF_(2)H as the difluoromethylation reagent,providing a facile access to difluoromethylarenes under mild reaction conditions without pre-generation of arylmetal reagents.展开更多
The electrophilic addition to an alkene with an electrophile has been widely studied and applied in organic synthesis.The organic chemistry textbook describes the classical reaction between an alkene and an iodine ele...The electrophilic addition to an alkene with an electrophile has been widely studied and applied in organic synthesis.The organic chemistry textbook describes the classical reaction between an alkene and an iodine electrophile(such as elemental iodine and N-iodosuccinimide(NIS))as a typical ionic reaction,in which an iodonium ion is formed and then attacked by a nucleophile.However,in this article,we report a new and unusual reaction mode between an alkene and NIS;that is,a single electron transfer(SET)process occurs between these two reactants by forming an electron-donor acceptor complex.Not only does this unusual single electron transfer reaction between an alkene and NIS add fundamentally important knowledge to organic chemistry,it also provides a valuable synthetic method as the new SET reaction mode with opposite regioselectivity as compared with the traditional ionic mode.展开更多
A copper-mediated di- and monoffuoromethanesulfonylation of arenediazonium tetrafluoroborates using di- and monofluoromethanesul- finate reagents provides aryl difluoromethyl （or monofluoromethyl） sulfones in 8ood y...A copper-mediated di- and monoffuoromethanesulfonylation of arenediazonium tetrafluoroborates using di- and monofluoromethanesul- finate reagents provides aryl difluoromethyl （or monofluoromethyl） sulfones in 8ood yields. It was found that the relative reactivity of these sodium fluoroalkanesulfinates in the present reactions decreases in the followin8 order： CH2FSO2Na 〉 CF2HSO2Na 〉 CF3SO2Na.展开更多
An improved method for the preparation of pentafluoroethylating reagent pentafluoroethyl-substituted benzio- doxole （BIX-C2Fs） was described. Under mild conditions, BIX-C2F5 was able to react with β-ketoesters or a...An improved method for the preparation of pentafluoroethylating reagent pentafluoroethyl-substituted benzio- doxole （BIX-C2Fs） was described. Under mild conditions, BIX-C2F5 was able to react with β-ketoesters or aryl/ heteroaryl boronic acids to generate pentafluoroethylated compounds in good yields.展开更多
An efficient nucleophilic difluoro(phenylsulfonimidoyl)methylation of unactivated primary alkyl bromides with PhSO(NTBS)CF_(2)H has been developed.It is particularly remarkable that,when 1.5 equiv.of alkyl bromides ar...An efficient nucleophilic difluoro(phenylsulfonimidoyl)methylation of unactivated primary alkyl bromides with PhSO(NTBS)CF_(2)H has been developed.It is particularly remarkable that,when 1.5 equiv.of alkyl bromides are used,the substitution products are obtained in moderate to excellent yields.The prepared difluoro(phenylsulfonimidoyl)methylated alkanes can be readily transformed to gem-difluoroalkenes via base-mediatedβ-elimination reaction.展开更多
Background and Originality Content Scheme I Aromatic pentafluoroethylation using TFE and CsF Perfluoroalkylated compounds are of great interest in pharmaceutical,agrochemical and material research and industry.[...Background and Originality Content Scheme I Aromatic pentafluoroethylation using TFE and CsF Perfluoroalkylated compounds are of great interest in pharmaceutical,agrochemical and material research and industry.[1]In this context,numerous efforts have been devoted to developing novel methods for the introduction of trifluoromethyl group(CF3)into organic aromatic compounds.[2]However,the similar pentafluoroethylation processes are still underexploited.[3] Currently available aromatic pentafluoroethylation methods mainly rely on transition-metal-mediated cross-coupling of aryl halides131 or aryl-boron compounds,141 and C-H functionalization of arenes.展开更多
1,1-Difluorinated sulfonamides are known to have better anti-inflammatory activity and enzyme inhibitory potency than their nonfluorinated counterparts.Two geminal fluorine atoms cause electronic perturbation of the n...1,1-Difluorinated sulfonamides are known to have better anti-inflammatory activity and enzyme inhibitory potency than their nonfluorinated counterparts.Two geminal fluorine atoms cause electronic perturbation of the nearby polar groups enhanced the biological activity of the 1,1-difluorinated sulfonamides.However,because methods for their stereoselective synthesis are scarce,such entities remain entirely unexplored.Here,we outline an efficient method for the stereoselective introduction of the difluoro(aminosulfonyl)methyl group(CF_(2)SO_(2)NH_(2))into carbonyls,imines,and alkyl halides with a new(R)-2-pyridyl difluoromethyl sulfoximine reagent,which provides a unique solution for the synthesis of chiralα,α-difluorinated sulfonamides with a quaternary stereocenter.Its potency is illustrated by the synthesis of fluorinated analogues of bioactive compounds such as 2-OH-SA,an antagonist for the GABA_(B)receptor in guinea pig ileum,and the late-stage modification of complex molecules such as haloperidol,ebastine,cholesterol,and(+)-δ-tocopherol derivatives.Stereoselective difluoro(aminosulfinyl)methylation to yield chiral sulfinylamides is presented,showcasing other uses of this new reagent.展开更多
基金supported by the National Key Research and Development Program of China(2021YFF0701700)the National Natural Science Foundation of China(22271299,22261132514)+1 种基金the Natural Science Foundation of Shandong Province(ZR2021LFG006)the State Key Laboratory of Fluorine-Containing Functional Membrane Materials。
文摘The divergent reductive cross-coupling with an ambident electrophile is rare.Previously,we demonstrated a nickel-catalyzed reductive 2-pyridination of aryl iodides with difluoromethyl 2-pyridyl sulfone(2-Py SO_(2)CF_(2)H)via selective C(sp^(2))-S bond cleavage of the sulfone by using a phosphine ligand.In this communication,we report a novel nickel-catalyzed reductive coupling of aryl iodides and 2-Py SO_(2)CF_(2)H reagent,which constitutes a new method for aromatic difluoromethylation.The use of a tridentate terpyridine ligand is pivotal for the selective C(sp^(3))-S bond cleavage of the sulfone.This method employs readily available nickel catalyst and 2-Py SO_(2)CF_(2)H as the difluoromethylation reagent,providing a facile access to difluoromethylarenes under mild reaction conditions without pre-generation of arylmetal reagents.
基金supported by National Key Research and Development Program of China(2021YFF0701700)the National Natural Science Foundationof China(22271299 and 22261132514).
文摘The electrophilic addition to an alkene with an electrophile has been widely studied and applied in organic synthesis.The organic chemistry textbook describes the classical reaction between an alkene and an iodine electrophile(such as elemental iodine and N-iodosuccinimide(NIS))as a typical ionic reaction,in which an iodonium ion is formed and then attacked by a nucleophile.However,in this article,we report a new and unusual reaction mode between an alkene and NIS;that is,a single electron transfer(SET)process occurs between these two reactants by forming an electron-donor acceptor complex.Not only does this unusual single electron transfer reaction between an alkene and NIS add fundamentally important knowledge to organic chemistry,it also provides a valuable synthetic method as the new SET reaction mode with opposite regioselectivity as compared with the traditional ionic mode.
基金Acknowledgement This work was supported by the National Key Research and Development Program of China （2015CB931900, 2016YFB0101200）, the National Natural Science Foundation of China （21632009, 21421002, 21472221, 21372246, 21302206）, the Key Programs of the Chinese Academy of Sciences （KGZD-EW- TO8）, the Key Research Program of Frontier Sciences of CAS （O.YZDJ-SSW-SLH049）, Shanghai Science and Technology program （15XD1504400）, and Youth Innovation Promotion Association CAS （2014231）.
文摘A copper-mediated di- and monoffuoromethanesulfonylation of arenediazonium tetrafluoroborates using di- and monofluoromethanesul- finate reagents provides aryl difluoromethyl （or monofluoromethyl） sulfones in 8ood yields. It was found that the relative reactivity of these sodium fluoroalkanesulfinates in the present reactions decreases in the followin8 order： CH2FSO2Na 〉 CF2HSO2Na 〉 CF3SO2Na.
基金National Basic Research Program of China （No. 2012CB821600）, National Natural Science Foundation of China （Nos. 21372247, 21572258, 21421002） and SIOC.
文摘An improved method for the preparation of pentafluoroethylating reagent pentafluoroethyl-substituted benzio- doxole （BIX-C2Fs） was described. Under mild conditions, BIX-C2F5 was able to react with β-ketoesters or aryl/ heteroaryl boronic acids to generate pentafluoroethylated compounds in good yields.
基金Support of our work by the National Basic Research Program of China(Nos.2012CB215500 and 2012CB821600)the NNSFC(No.21372246)+1 种基金Shanghai QMX program(No.13QH1402400)the Chinese Academy of Sciences is gratefully acknowledged.
文摘An efficient nucleophilic difluoro(phenylsulfonimidoyl)methylation of unactivated primary alkyl bromides with PhSO(NTBS)CF_(2)H has been developed.It is particularly remarkable that,when 1.5 equiv.of alkyl bromides are used,the substitution products are obtained in moderate to excellent yields.The prepared difluoro(phenylsulfonimidoyl)methylated alkanes can be readily transformed to gem-difluoroalkenes via base-mediatedβ-elimination reaction.
基金This work was supported by the National Basic Research Program of China(Nos.2015CB931900,2012CB215500)the National Natural Science Foundation of China(Nos.21632009,21421002)+2 种基金the Key Program of the Chinese Academy of Sciences(No.KGZD-EW-T08)the Key Research Program of Frontier Sciences of CAS(No.QYZDJ-SSWSLH049)the Shanghai Rising-Star Program(No.16QA1404600)for financial support.
文摘Background and Originality Content Scheme I Aromatic pentafluoroethylation using TFE and CsF Perfluoroalkylated compounds are of great interest in pharmaceutical,agrochemical and material research and industry.[1]In this context,numerous efforts have been devoted to developing novel methods for the introduction of trifluoromethyl group(CF3)into organic aromatic compounds.[2]However,the similar pentafluoroethylation processes are still underexploited.[3] Currently available aromatic pentafluoroethylation methods mainly rely on transition-metal-mediated cross-coupling of aryl halides131 or aryl-boron compounds,141 and C-H functionalization of arenes.
基金the National Natural Science Foundation of China(51673199 and 51677176)Youth Inn ovation Promotion Association of Chinese Academy of Sciences(2015148)+4 种基金Dalian National Laboratory for Clean Energy(DNL180307)Innovation Foundation of Dalian Institute of Chemical PhysicsChinese Academy of Sciences(ZZBS201615 and ZZBS201708)Dalian Science and Technology Star Program(2016RQ026)The authors also thank Lei Shi for the helpful discussion on Li3N related reaction.
基金the National Key Research and Development Program of China (Nos.2015CB931900, 2016YFB0101200)the National Natural Science Foundation of China (Nos.21632009,21421002,21472221)+2 种基金the Key Programs of the Chinese Academy of Sciences (No.KGZD-EW-T08)the Key Research Program of Frontier Sciences of CAS (No.QYZDJ-SSW-SLH049)Shanghai Science and Technology program (No. 16QA1404600).
基金Financial support was provided by the National Key Research and Development Program of China(no.2016YFB0101200)the National Natural Science Foundation of China(no.21632009)+2 种基金the Key Programs of CAS(no.KGZD-EW-T08)the Key Research Program of Frontier Sciences of CAS(no.QYZDJ-SSW-SLH049)Shanghai Science and Technology Program(no.16QA1404600).
文摘1,1-Difluorinated sulfonamides are known to have better anti-inflammatory activity and enzyme inhibitory potency than their nonfluorinated counterparts.Two geminal fluorine atoms cause electronic perturbation of the nearby polar groups enhanced the biological activity of the 1,1-difluorinated sulfonamides.However,because methods for their stereoselective synthesis are scarce,such entities remain entirely unexplored.Here,we outline an efficient method for the stereoselective introduction of the difluoro(aminosulfonyl)methyl group(CF_(2)SO_(2)NH_(2))into carbonyls,imines,and alkyl halides with a new(R)-2-pyridyl difluoromethyl sulfoximine reagent,which provides a unique solution for the synthesis of chiralα,α-difluorinated sulfonamides with a quaternary stereocenter.Its potency is illustrated by the synthesis of fluorinated analogues of bioactive compounds such as 2-OH-SA,an antagonist for the GABA_(B)receptor in guinea pig ileum,and the late-stage modification of complex molecules such as haloperidol,ebastine,cholesterol,and(+)-δ-tocopherol derivatives.Stereoselective difluoro(aminosulfinyl)methylation to yield chiral sulfinylamides is presented,showcasing other uses of this new reagent.
