In recent years,the direct introduction of sulfonyl and sulfenyl groups into unsaturated substrates by using thiosulfonates as unique dual functional reagents has inarguably provided chemists a new platform for the di...In recent years,the direct introduction of sulfonyl and sulfenyl groups into unsaturated substrates by using thiosulfonates as unique dual functional reagents has inarguably provided chemists a new platform for the diverse synthesis of important S-containing derivatives.These 1,n-thiosulfonylation reactions usually feature simple procedures,100%atom economy,and high regioselectivity.This review focuses on the recent advancements in the transformations of thiosulfonates through 1,n-thiosulfonylation involving the formation of two distinct C-S bonds under transition-metal-catalyzed or metal-free conditions,where thiosulfonates act as both a sulfonyl and a sulfenyl component.展开更多
With the blossom of DNA encoded library(DEL)and nucleic acid aptamer techniques,DNA-compatible reactions draw increasing attention in both the pharmaceutical industry and academia.In this regard,the incorporation of o...With the blossom of DNA encoded library(DEL)and nucleic acid aptamer techniques,DNA-compatible reactions draw increasing attention in both the pharmaceutical industry and academia.In this regard,the incorporation of organosulfur scaffolds on DNA via the Csp2-S bond exhibits advantages but remains underrepresented.Herein,we report a mild and efficient photoredox atom transfer radical addition(ATRA)to terminal and internal alkynes with thiosulfonates catalyzed by organic photocatalyst,furnishing a wide array of E-β-arylthiol-vinyl sulfones with excellent regio-and stereoselectivity.Mechanistic investigations demonstrate that sulfonyl radical likely served as the key intermediate in this transformation.Leveraging the broad functional group tolerance and the mild and biofriendly conditions,this protocol could be adapted to simultaneously install sulfones and sulfides on DNA.More importantly,a redox-responsive fluorescent probe(10-ethyl-2-sulfonate-acridone,ESAC)could be conveniently introduced on two commonly used aptamers(AS1411 and Sgc8c),allowing their subsequent imaging studies across a series of human tumor cell lines.Remarkably,the process of ESAC-aptamers entering the cells was captured by both confocal microscopy and flow cytometry techniques,whereby most of the ESAC-aptamers exhibited green fluorescence after their cellular uptake,with the small portion remaining in the outer membrane emitting blue fluorescence.展开更多
A desulfonylative thiolation between heteroaryl sulfones and thiosulfonates for the efficient synthesis of heteroaryl sulfides was developed.The cross-electrophile couplings proceeded effectively via old C–SO_(2) bon...A desulfonylative thiolation between heteroaryl sulfones and thiosulfonates for the efficient synthesis of heteroaryl sulfides was developed.The cross-electrophile couplings proceeded effectively via old C–SO_(2) bond cleavage and new C–S bond formation in the presence of cheapest and widely available iron powder as mediator under transition metal catalyst-free conditions,leading to a wide array of heteroaryl sulfides derived from benzo[d]thiazole,benzo[d]oxazole,thiazole,1,3,4-thiadiazole,and 1H-tetrazole in modest to excellent yields.In addition,the reaction exhibited good functional group compatibility,and the protocol could also be applicable to the use of selenosulfonate as substrate and be subjected to scale-up synthesis with equal ease.Notably,unreacted iron powder could be readily recovered after reaction by resorting to the attracting property of magnetic stir bar to iron.展开更多
A visible-light-induced and efficient one-pot synthesis ofβ-hydroxysulfides from olefins,thiosulfonates and HCOOCs using an EDA complex strategy under air atmosphere at room temperature has been disclosed.A plausible...A visible-light-induced and efficient one-pot synthesis ofβ-hydroxysulfides from olefins,thiosulfonates and HCOOCs using an EDA complex strategy under air atmosphere at room temperature has been disclosed.A plausible radical involved mechanism is proposed.During the reaction process,formates play a crucial role:first,as donors in the EDA complex;second,as providers of the hydrogen source;and third,by generating CO_(2)^(•–)to reduce peroxide intermediates,leading to the formation ofβ-hydroxysulfides.In contrast to the previously reported thiol-oxygen co-oxidation reactions,this simple and sustainable approach features mild reaction conditions,operational simplicity,odorless and excellent functional group tolerance.展开更多
A highly practical method to access unsymmetrical and symmetrical thiosulfonates in moderate to excellent yields has been developed through NBS-promoted sulfenylation of sulfinates with disulfides. The present process...A highly practical method to access unsymmetrical and symmetrical thiosulfonates in moderate to excellent yields has been developed through NBS-promoted sulfenylation of sulfinates with disulfides. The present process enables the use of two RS in RSSR and shows broad functional group tolerance, which represents an atom-economical and practical procedure for the synthesis of thiosulfonates. A plausible mechanism for the role of NBS as a promoter for the cleavage of disulfides generating N-（organothio）succinimide that then undergos facile sulenylation with sulfinates is proposed.展开更多
A TFA promoted multi-component reaction of aryldiazonium with sodium metabisulphite and thiols to construct thiosulfonates under transition-metal free conditions is reported.The thiosulfonates were isolated in good yi...A TFA promoted multi-component reaction of aryldiazonium with sodium metabisulphite and thiols to construct thiosulfonates under transition-metal free conditions is reported.The thiosulfonates were isolated in good yields with broad tolerance of functional group.Readily available inorganic Na2S2O5 was applied as the sulfur dioxide surrogate.This strategy features easily available substrates,mild reaction conditions and free transition-metal catalyst.展开更多
基金financial support from the Natural Science Foundation of China(No.22001121)Natural Science Foundation of Jiangsu Province(No.BK20180690)+1 种基金Nanjing Tech University(Start-up Grant Nos.39837118 and39837146)Xuzhou Medical University(Start-up Grant No.RC20552038)。
文摘In recent years,the direct introduction of sulfonyl and sulfenyl groups into unsaturated substrates by using thiosulfonates as unique dual functional reagents has inarguably provided chemists a new platform for the diverse synthesis of important S-containing derivatives.These 1,n-thiosulfonylation reactions usually feature simple procedures,100%atom economy,and high regioselectivity.This review focuses on the recent advancements in the transformations of thiosulfonates through 1,n-thiosulfonylation involving the formation of two distinct C-S bonds under transition-metal-catalyzed or metal-free conditions,where thiosulfonates act as both a sulfonyl and a sulfenyl component.
基金the following institutions for their financial support:T.J.thanks Guangdong Basic and Applied Basic Research Foundation,China(grant nos.2021B1515120046 and 2022B1515120075)the Science and Technology Innovation Commission of Shenzhen Municipality,China(grant nos.JCYJ20220818101404010 and 20220815113214003)+4 种基金High-Level of Special Funds,China(grant no.G03050K003)the National Natural Science Foundation of China(grant no.22078263)the National Key R&D Program of China(grant no.2022YFC2106100)the Hunan Provincial Science Foundation for Distinguished Young Scholars,China(grant no.2022JJ10005)the Key Science and Technology project of Hunan Province,China(grant no.2021SK1020).
文摘With the blossom of DNA encoded library(DEL)and nucleic acid aptamer techniques,DNA-compatible reactions draw increasing attention in both the pharmaceutical industry and academia.In this regard,the incorporation of organosulfur scaffolds on DNA via the Csp2-S bond exhibits advantages but remains underrepresented.Herein,we report a mild and efficient photoredox atom transfer radical addition(ATRA)to terminal and internal alkynes with thiosulfonates catalyzed by organic photocatalyst,furnishing a wide array of E-β-arylthiol-vinyl sulfones with excellent regio-and stereoselectivity.Mechanistic investigations demonstrate that sulfonyl radical likely served as the key intermediate in this transformation.Leveraging the broad functional group tolerance and the mild and biofriendly conditions,this protocol could be adapted to simultaneously install sulfones and sulfides on DNA.More importantly,a redox-responsive fluorescent probe(10-ethyl-2-sulfonate-acridone,ESAC)could be conveniently introduced on two commonly used aptamers(AS1411 and Sgc8c),allowing their subsequent imaging studies across a series of human tumor cell lines.Remarkably,the process of ESAC-aptamers entering the cells was captured by both confocal microscopy and flow cytometry techniques,whereby most of the ESAC-aptamers exhibited green fluorescence after their cellular uptake,with the small portion remaining in the outer membrane emitting blue fluorescence.
基金We gratefully acknowledge the financial support from Nanjing Tech University(Start-up Grant No.39837118).
文摘A desulfonylative thiolation between heteroaryl sulfones and thiosulfonates for the efficient synthesis of heteroaryl sulfides was developed.The cross-electrophile couplings proceeded effectively via old C–SO_(2) bond cleavage and new C–S bond formation in the presence of cheapest and widely available iron powder as mediator under transition metal catalyst-free conditions,leading to a wide array of heteroaryl sulfides derived from benzo[d]thiazole,benzo[d]oxazole,thiazole,1,3,4-thiadiazole,and 1H-tetrazole in modest to excellent yields.In addition,the reaction exhibited good functional group compatibility,and the protocol could also be applicable to the use of selenosulfonate as substrate and be subjected to scale-up synthesis with equal ease.Notably,unreacted iron powder could be readily recovered after reaction by resorting to the attracting property of magnetic stir bar to iron.
基金National Natural Science Foundation of China(Grant Nos.21901216 and 21871031)the Funds of Sichuan Science and Technology Program(Nos.23NSFSC0862 and 2023NSFSC0104)the Fundamental Research Funds for the Central Universities(No.2682023ZTPY003).
文摘A visible-light-induced and efficient one-pot synthesis ofβ-hydroxysulfides from olefins,thiosulfonates and HCOOCs using an EDA complex strategy under air atmosphere at room temperature has been disclosed.A plausible radical involved mechanism is proposed.During the reaction process,formates play a crucial role:first,as donors in the EDA complex;second,as providers of the hydrogen source;and third,by generating CO_(2)^(•–)to reduce peroxide intermediates,leading to the formation ofβ-hydroxysulfides.In contrast to the previously reported thiol-oxygen co-oxidation reactions,this simple and sustainable approach features mild reaction conditions,operational simplicity,odorless and excellent functional group tolerance.
基金Supporting intbrmation tbr this article is available on the WWW under http：//dx.doi.org/10.1002/cjoc.201200028 or from the author.Acknowledgement This work was supported by the National Natural Science Foundation of China （Nos. 21102105 and 21072153）.
文摘A highly practical method to access unsymmetrical and symmetrical thiosulfonates in moderate to excellent yields has been developed through NBS-promoted sulfenylation of sulfinates with disulfides. The present process enables the use of two RS in RSSR and shows broad functional group tolerance, which represents an atom-economical and practical procedure for the synthesis of thiosulfonates. A plausible mechanism for the role of NBS as a promoter for the cleavage of disulfides generating N-（organothio）succinimide that then undergos facile sulenylation with sulfinates is proposed.
基金the National Natural Science Foundation of China(Nos.21971174,21772137,21672157)the PhD Programs Foundation of PAPD+2 种基金the Project of Scientific and Technologic Infrastructure of Suzhou(No.SZS201708)the Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions(No.16KJA150002)Soochow University,and State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials for financial support。
文摘A TFA promoted multi-component reaction of aryldiazonium with sodium metabisulphite and thiols to construct thiosulfonates under transition-metal free conditions is reported.The thiosulfonates were isolated in good yields with broad tolerance of functional group.Readily available inorganic Na2S2O5 was applied as the sulfur dioxide surrogate.This strategy features easily available substrates,mild reaction conditions and free transition-metal catalyst.
