Using 2-[bis（alkylthio）methylene]-3-oxo-N-o-tolylbutanamides 1 as odorless thiol equivalents, an efficient and odorless synthesis of thioethers has been developed. Promoted by NaOH in EtOH, the cleavage of 1 commenc...Using 2-[bis（alkylthio）methylene]-3-oxo-N-o-tolylbutanamides 1 as odorless thiol equivalents, an efficient and odorless synthesis of thioethers has been developed. Promoted by NaOH in EtOH, the cleavage of 1 commences to generate thiolate anions, and the generated thiolate anions then react with halides to give various thioethers in good yield. It is noteworthy that only a very faint odor ofthiols can be perceived during both the reaction and the workup.展开更多
The disulfides reacted with zinc in DMF, followed by alkyl halides, giving unsymmetrical thioether in excellent yields. This reaction takes place under mild and neutral conditions.
Tetrabutylammonium fluoride （TBAF） effectively facilitated a denitrative substitution reaction of electron-deficient nitroarenes with phenylthiotrimethylsilane （PhSTMS） under mild and base-free neutral conditions ...Tetrabutylammonium fluoride （TBAF） effectively facilitated a denitrative substitution reaction of electron-deficient nitroarenes with phenylthiotrimethylsilane （PhSTMS） under mild and base-free neutral conditions at room temperature, providing a practical and efficient synthesis of useful unsymmetrical diaryl thioethers. Nitroarenes bearing ortho- and para-positioned electron-withdrawing groups are the most reactive substrates, indicating that this reaction most possibly proceeded via the nucleophilic aromatic substitution （SNAr） mechanism.展开更多
Some new asymmetric thioethers 5 and 4-thiazolidinones 6 have been obtained from condensation of 5-formyl-3-(pyridin-4'-yl)-1,2,4-triazino[5,6-b] indole (3) with halogenated aromatic amines followed by addition of...Some new asymmetric thioethers 5 and 4-thiazolidinones 6 have been obtained from condensation of 5-formyl-3-(pyridin-4'-yl)-1,2,4-triazino[5,6-b] indole (3) with halogenated aromatic amines followed by addition of thiophenol and/or cycloaddition with thiolactic acids in nonpolar solvents. Structures of the products confirmed by elemental analysis and spectral measurements. The new systems obtained were evaluated as antifungal agents.展开更多
The development of heterogeneous molecule-based catalysts for red light-mediated photocatalysis is still challenging due to the improper light absorption for most materials and the photoactivity deactivation for solid...The development of heterogeneous molecule-based catalysts for red light-mediated photocatalysis is still challenging due to the improper light absorption for most materials and the photoactivity deactivation for solid assembly.Herein,red light photocatalysis with a hydrogen-bonded organic framework(HOF)is established.This HOF,named HOF-66,is formed from the self-assembly of guanine-decorated naphthalenediimide(NDI)molecule through hydrogen-bonded guanine-quadruplex nodes,showing square grid supramolecular layers confirmed by powder X-ray diffraction analysis.In contrast to unsubstituted NDI HOF,introduction of ethylamino groups to NDI core in HOF-66 tunes strong electronic maximum absorption peak to 619 nm,allowing red light photocatalysis of singlet oxygen evolution proved by 1,3-diphenylisobenzofuran degradation and electron spin resonance determination.Particularly,under the same conditions,the sulfide oxidation rate in the presence of HOF-66 was 28 times higher compared to its unsubstituted analogue.This work integrates the molecular design and aggregation effect towards the application of HOFs,opening a new gate for red light photocatalysts.展开更多
A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpolung C–S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides to produce alkyl...A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpolung C–S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides to produce alkyl aryl thioethers is described. This reaction features excellent selectivity, wide functionality tolerance, broad substrate scope, and facile late-stage modification of biologically relevant molecules.Mechanistic studies recognize initial generation of an amidyl radical anion via thermoinduced reduction of DMF with Sn, followed by umpolung reduction and single electron transfer of the nucleophilic sulfonyl moiety to form a sulphydryl radical and engage the Ni^(0)/Ni^(Ⅰ)/Ni^(Ⅲ)/Ni^(I) catalytic cycle.展开更多
基金This work was supported by the National Natural Science Foundation of China （No. 20572013） and the Doctoral Foundation of Anshan Normal University.
文摘Using 2-[bis（alkylthio）methylene]-3-oxo-N-o-tolylbutanamides 1 as odorless thiol equivalents, an efficient and odorless synthesis of thioethers has been developed. Promoted by NaOH in EtOH, the cleavage of 1 commences to generate thiolate anions, and the generated thiolate anions then react with halides to give various thioethers in good yield. It is noteworthy that only a very faint odor ofthiols can be perceived during both the reaction and the workup.
文摘The disulfides reacted with zinc in DMF, followed by alkyl halides, giving unsymmetrical thioether in excellent yields. This reaction takes place under mild and neutral conditions.
基金the National Natural Science Foundation of China(No.20902070)Natural Science Foundation of Zhejiang Province(No.Y4100579)Qianjiang Talents Program of Zhejiang Province(No.QJD0902004) for financial supports
文摘Tetrabutylammonium fluoride （TBAF） effectively facilitated a denitrative substitution reaction of electron-deficient nitroarenes with phenylthiotrimethylsilane （PhSTMS） under mild and base-free neutral conditions at room temperature, providing a practical and efficient synthesis of useful unsymmetrical diaryl thioethers. Nitroarenes bearing ortho- and para-positioned electron-withdrawing groups are the most reactive substrates, indicating that this reaction most possibly proceeded via the nucleophilic aromatic substitution （SNAr） mechanism.
文摘Some new asymmetric thioethers 5 and 4-thiazolidinones 6 have been obtained from condensation of 5-formyl-3-(pyridin-4'-yl)-1,2,4-triazino[5,6-b] indole (3) with halogenated aromatic amines followed by addition of thiophenol and/or cycloaddition with thiolactic acids in nonpolar solvents. Structures of the products confirmed by elemental analysis and spectral measurements. The new systems obtained were evaluated as antifungal agents.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22011540002 and 22131005)Xiaomi Young Scholar Program,the Fundamental Research Funds for the Central Universities,the Advanced Talents Incubation Program of Hebei University,and University of Science and Technology Beijing and Hebei University are gratefully acknowledged.
文摘The development of heterogeneous molecule-based catalysts for red light-mediated photocatalysis is still challenging due to the improper light absorption for most materials and the photoactivity deactivation for solid assembly.Herein,red light photocatalysis with a hydrogen-bonded organic framework(HOF)is established.This HOF,named HOF-66,is formed from the self-assembly of guanine-decorated naphthalenediimide(NDI)molecule through hydrogen-bonded guanine-quadruplex nodes,showing square grid supramolecular layers confirmed by powder X-ray diffraction analysis.In contrast to unsubstituted NDI HOF,introduction of ethylamino groups to NDI core in HOF-66 tunes strong electronic maximum absorption peak to 619 nm,allowing red light photocatalysis of singlet oxygen evolution proved by 1,3-diphenylisobenzofuran degradation and electron spin resonance determination.Particularly,under the same conditions,the sulfide oxidation rate in the presence of HOF-66 was 28 times higher compared to its unsubstituted analogue.This work integrates the molecular design and aggregation effect towards the application of HOFs,opening a new gate for red light photocatalysts.
基金the National Natural Science Foundation of China(No.22271245)the Jiangxi Province Science and Technology Project(Nos.20212AEI91002 and 20202ACBL213002)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(No.2021ZD01)for financial support.
文摘A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpolung C–S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides to produce alkyl aryl thioethers is described. This reaction features excellent selectivity, wide functionality tolerance, broad substrate scope, and facile late-stage modification of biologically relevant molecules.Mechanistic studies recognize initial generation of an amidyl radical anion via thermoinduced reduction of DMF with Sn, followed by umpolung reduction and single electron transfer of the nucleophilic sulfonyl moiety to form a sulphydryl radical and engage the Ni^(0)/Ni^(Ⅰ)/Ni^(Ⅲ)/Ni^(I) catalytic cycle.
