Sulfonylation is extensively used to label DNA and RNA,assess their interactions,and quantify components including nucleobases and nucleosides/nucleotides although the sulfonylation sites remain controversial.Here,we ...Sulfonylation is extensively used to label DNA and RNA,assess their interactions,and quantify components including nucleobases and nucleosides/nucleotides although the sulfonylation sites remain controversial.Here,we systematically investigated the sulfonylation of adenine(ade)and its nucleosides/nucleotides with 5-(dimethylamino)-naphthalene-1-sulfonyl chloride(DNS-Cl),5-(diethylamino)-naphthalene-1-sulfonyl chloride(DEANS-Cl),and 5-((N,N-diethylleucyl)amino)-naphthalene-1-sulfonyl chloride(DELANS-Cl).Detailed spectral analysis with nuclear magnetic resonance(NMR)spectroscopy and high-resolution mass spectrometry(HRMS)showed similar sulfonylation behaviors among the reagents.For ade,its secondary amine in the imidazole ring(N9 H)sulfonylated more readily than the exocyclic amino group(N6 H2).For adenosine and its nucleotides,the 20-OH group in the ribosyl moiety was preferably sulfonylated,whereas the 30-OH was the preferred site for 20-deoxyadenosine and its nucleotides.Alkylation and amidation of the aromatic amino group in these 5-amino-naphthalene-1-sulfonyl chlorides did not influence the sulfonylation preferences.This offered a reliable approach and comprehensive details of such sites for ade and its nucleosides/nucleotides.展开更多
An eco-friendly protocol for the synthesis of various 2-sulfonyl quinolines/pyridines through sulfonylation of heteroaromatic N-oxides with sodium sulfinates in water at ambient temperature under metal-and oxidant-fre...An eco-friendly protocol for the synthesis of various 2-sulfonyl quinolines/pyridines through sulfonylation of heteroaromatic N-oxides with sodium sulfinates in water at ambient temperature under metal-and oxidant-free conditions has been developed.The mild reaction conditions,high reaction efficiency,operational simplicity,short reaction time and remarkable functional-group compatibility make the developed protocol very attractive for the preparation of 2-sulfonyl N-heteroaromatic compounds.展开更多
A visible-light-mediated reaction of indole derivatives employing arylsulfonyl chlorides as sulfonyl surrogates has been developed,which proceeds via the sequence of reduction of sulfonyl chloride,sulfonylation,and in...A visible-light-mediated reaction of indole derivatives employing arylsulfonyl chlorides as sulfonyl surrogates has been developed,which proceeds via the sequence of reduction of sulfonyl chloride,sulfonylation,and intramolecular cyclization.This mild protocol transforms a diverse array of indole tethered alkenes and simple sulfonyl chlorides into highly valuable functionalized tetrahydrocarbazoles in good yields.This reaction is also suitable for gram-scale synthesis,which provides an efficient and green access to multi-substituted tetrahydrocarbazoles.展开更多
The perfluoroalkylsulfonylation(CF_(3)SO_(2),C_(2)F_(5)SO_(2)and CHF_(2)SO_(2))in the enaminone C-H bonds has been developed simply via the promotion of molecular iodine by using stable and cheap sodium perfluoroalkyl...The perfluoroalkylsulfonylation(CF_(3)SO_(2),C_(2)F_(5)SO_(2)and CHF_(2)SO_(2))in the enaminone C-H bonds has been developed simply via the promotion of molecular iodine by using stable and cheap sodium perfluoroalkyl sulfinates as coupling partners.The stereoselective synthesis of E-configuratedα-perfluoroalkylsulfonyl enaminones has been realized via unprecedented C-H bond elaboration and C=C double bond configuration inversion by free radical process.展开更多
The development of practical methods for the direct and selective C(sp^(3))‒H functionalization of hydrocarbons is an attractive topic in synthetic chemistry.Although the radical‐mediated hydrogen atom transfer(HAT)p...The development of practical methods for the direct and selective C(sp^(3))‒H functionalization of hydrocarbons is an attractive topic in synthetic chemistry.Although the radical‐mediated hydrogen atom transfer(HAT)process has shown considerable potential in such reactions,it still faces fundamental problems associated with reactivity and selectivity.Herein,we report a convenient and economic approach to site‐selective C(sp^(3))‒H sulfonylation via photo‐induced HAT catalysis.Employing a conjugated polycyclic quinone as a direct HAT photocatalyst,commercially available inorganic sulfinates as the sulfonylation source,copper triflate as an inexpensive oxidant,a variety of toluene derivatives and cycloalkanes were converted into biologically and synthetically interesting sulfone products under mild conditions.The mechanistic studies reveal that the reaction sequence involves direct HAT‐induced radical formation and a subsequent copper‐mediated organometallic process for the C‒S bond formation.This method offers an appealing opportunity to furnish high value‐added products from abundant hydrocarbon starting materials and inexpensive reagents.展开更多
A new and convenient procedure is developed for the preparation of N-sulfonylbenzotriazoles from sodium sulfinates and benzotriazoles using molecular iodine as catalyst via the S-N bond formation reaction. This cataly...A new and convenient procedure is developed for the preparation of N-sulfonylbenzotriazoles from sodium sulfinates and benzotriazoles using molecular iodine as catalyst via the S-N bond formation reaction. This catalytic radical sulfonylation proceeds efficiently in air at room temperature under neutral conditions, and in short reaction time, to afford the corresponding N-sulfonylbenzotriazoles in good yields, thus extending the catalytic application of molecular iodine in organic synthesis.展开更多
A convenient and regioselective sulfonylation/cyclization of 1,6-enynes with arylazo sulfones has been developed to access a series of sulfonylated γ-butyrolactams.The present reaction could be efficiently conducted ...A convenient and regioselective sulfonylation/cyclization of 1,6-enynes with arylazo sulfones has been developed to access a series of sulfonylated γ-butyrolactams.The present reaction could be efficiently conducted under catalyst-and additive-free conditions,in which C-S and C-C bonds were selectively constructed in one-pot procedure.展开更多
Enantioselective intramolecular radical difunctionalization of alkenes involving sulfur dioxide through a three-component reaction of 4-arylpent-4-enoic acids,sodium hydrogen sulfite and thianthrenium salts under copp...Enantioselective intramolecular radical difunctionalization of alkenes involving sulfur dioxide through a three-component reaction of 4-arylpent-4-enoic acids,sodium hydrogen sulfite and thianthrenium salts under copper catalysis and photocatalysis is reported,allowing the construction of chiral 5-((sulfonyl)methyl)dihydrofuran-2(3H)-ones with β-quaternary stereocenters.During the transformation,sodium hydrogen sulfite is used as the sulfur dioxide surrogate.Excellent enantiocontrol(up to 99%ee)and wide functional group compatibility are observed in this asymmetric radical sulfonylation.展开更多
By employing a readily available CuCI/DDQ catalyst system,we herein report a direct C(sp^(3))-H sulfonylation of xanthene derivates with odorless sodium sulfinates.Various 9H-xanthenes,thioxanthenes,and 9,10-dihydroac...By employing a readily available CuCI/DDQ catalyst system,we herein report a direct C(sp^(3))-H sulfonylation of xanthene derivates with odorless sodium sulfinates.Various 9H-xanthenes,thioxanthenes,and 9,10-dihydroacridines are efficiently transformed into the desired benzylic sulfonyl products via a radical/radical cross-coupling process,proceeding with the merits of broad substrate scope,operational simplicity,good functional group compatibility,and mild reaction conditions.展开更多
Comprehensive Summary The selective oxidative sulfonylation of alkenes with selenium sulfonate depended on the reaction conditions.The electrochemical C—H sulfonylation proceeded smoothly to afford(E)-vinyl sulfones ...Comprehensive Summary The selective oxidative sulfonylation of alkenes with selenium sulfonate depended on the reaction conditions.The electrochemical C—H sulfonylation proceeded smoothly to afford(E)-vinyl sulfones with good selectivity in an undivided cell without external oxidant.While aerobic trifunctionalization of alkenes occurred in the presence of KI in the air,which providesβ-keto selenosulfones via the formation of C—O,C—S,and C—Se bonds in one-pot.Following control experiments,a plausible mechanism is proposed to rationalize the experimental results.展开更多
Herein, we reported an efficient and straightforward method to realize desaturated β-C(sp^(3))-H sulfonylation andphosphonylation of cyclic amines driven by electrochemistry using catalytic amounts of CP_(2)Fe as the...Herein, we reported an efficient and straightforward method to realize desaturated β-C(sp^(3))-H sulfonylation andphosphonylation of cyclic amines driven by electrochemistry using catalytic amounts of CP_(2)Fe as the redoxmediator. This protocol which had good functional group compatibility, provided the desired enaminyl sulfoneand enaminyl phosphine oxide products with high chemo- and regio-selectivity under mild conditions. Severalmechanistic studies have suggested that cyclic amines underwent multiple single-electron oxidation and deprotonation processes, followed by a capture step involving either a sulfonyl radical or a phosphonyl radical, ultimately leading to the desired products.展开更多
Tunable photoredox-catalyzed chlorosulfonylation and oxysulfonylation ofα-trifluoromethylstyrenes with sulfonyl chloride were facilely achieved by simply manipulating the photocatalyst and solvent.This strategy makes...Tunable photoredox-catalyzed chlorosulfonylation and oxysulfonylation ofα-trifluoromethylstyrenes with sulfonyl chloride were facilely achieved by simply manipulating the photocatalyst and solvent.This strategy makes full use of the structural features of sulfonyl chloride to afford diverse bifunctional products ofα-trifluoromethylstyrenes in up to 95%yield with excellent functional group tolerance.展开更多
Organosilanes are not found in nature but play a crucial role in the sustainable development of modern society.Si-chiral organosilanes represent a type of novel chemical space that is highly desirable for research ori...Organosilanes are not found in nature but play a crucial role in the sustainable development of modern society.Si-chiral organosilanes represent a type of novel chemical space that is highly desirable for research oriented in terms of their properties,including synthetic chemistry,drug discovery,and materials and life sciences.While much effort has been given to the catalytic enantioselective construction of Si-chirality,the facile synthesis of multifunctional Si-chiral silanes remains undeveloped.Here,we report an unprecedented highly enantioselective copper-catalyzed desymmetric sulfonylation or acylation of prochiral 1,3-siladiols for the expedient synthesis of multifunctional Si-chiral silanes with both a hydroxymethyl group and an ester group as synthetic handles.A one-pot tandem desymmetric sulfonylation/substitution sequence,internally reusing waste chloride or bromide formed from the upstream sulfonylation step as the reagent for a substitution step,is also exploited for the atom-efficient synthesis of Si-chiral silylmethanols featuring a chloromethyl or bromomethyl group.A newly developed sterically confined pyridine-bis(oxazoline)(PYBOX)ligand with a bulky C4 amide-containing shielding group is crucial for achieving excellent reactivity and enantioselectivity.The scale-up synthesis and various diversifying elaborations of multifunctional Si-chiral silylmethanols further highlight the synthetic practicability of this protocol.展开更多
Sulfur-containing organic compounds display wide applications in the field of materials science,synthetic chemistry,and pharmaceutical industry.Thus,numerous synthetic strategies have been developed for the synthesis ...Sulfur-containing organic compounds display wide applications in the field of materials science,synthetic chemistry,and pharmaceutical industry.Thus,numerous synthetic strategies have been developed for the synthesis of sulfur-containing compounds in synthetic chemistry.In recent years,the utilization of sulfinic acids as versatile synthons has emerged as attractive and powerful approach to access various organosulfur compounds through sulfonylation,sulfinylation or sulfenylation reactions.In this review,we summarized the recent progress in the construction of various sulfur-containing compounds from sulfininc acids.Selected examples of substrates and the related reaction mechanisms are described here.This review intends to provide readers a comprehensive understanding on the synthesis of sulfur-containing molecules from sulfinic acids and provide help for future synthetic research.展开更多
N,N’-Disulfonylhydrazines have been proven to be the most reactive precursors of the sulfonyl radicals among all types of sulfonyl substituted hydrazines as early as half a century ago.However,the sulfonyl radicals g...N,N’-Disulfonylhydrazines have been proven to be the most reactive precursors of the sulfonyl radicals among all types of sulfonyl substituted hydrazines as early as half a century ago.However,the sulfonyl radicals generated from these compounds have not been used in organic synthesis except the simple selfdimerization synthesis of disulfones controlled by the"solvent-cage-effects".In this article,N,N’-disulfonylhydrazines were introduced as new sulfonylating reagents and their combinations with NIS were disclosed as new iodosulfonylating reagents of allcynes.Finally,a highly efficient method for the synthesis of(E)-β-iodovinyl arenesulfones was developed by mixing an alkyne,a N,N’-disulfonylhydrazine and NIS in aqueous THF at room temperature for 5 min.展开更多
Several bis（trifluoromethylsulfonyl）phenylamines have been synthesized and used as internal donors for the preparation of heterogeneous Ziegler-Natta catalysts for propylene polymerization. These new cata- lysts are...Several bis（trifluoromethylsulfonyl）phenylamines have been synthesized and used as internal donors for the preparation of heterogeneous Ziegler-Natta catalysts for propylene polymerization. These new cata- lysts are highly active and stereospecific in combination with an external donor for the polymerization of propylene. The activity of these catalysts is dramatically influenced by the electronic capability of the phenyl substituents on the sulfonyl phenylamines. Therefore, the performances of the catalysts can be modified by adjusting the electronic property of the phenyl substituents of the sulfonyl phenylamines.展开更多
Composite polymer electrolytes based on mixing soft-segment waterborne polyurethane （WPU） and 1-butyl-3-methylimidazolium bis[（trifluoromethyl）sulfonyl]imide （BMImTFSI） have been prepared and characterized. The ...Composite polymer electrolytes based on mixing soft-segment waterborne polyurethane （WPU） and 1-butyl-3-methylimidazolium bis[（trifluoromethyl）sulfonyl]imide （BMImTFSI） have been prepared and characterized. The addition of BMImTFSI results in an increase of the ionic conductivity. At high BMImTFSI concentration （BMImTFSI/WPU = 3 in weight ratio）, the ionic conductivity reaches 4.27 × 10^-3 S/cm at 30 ℃. These composite polymer electrolytes exhibit good thermal and electrochemical stability, which are high enough to be applied in lithium batteries.展开更多
A simple and efficient method for the synthesis of pyrazoles through a silicotungstic acid (H_(4)SiW_(12)O_(40))-catalyzed cyclization of epoxides/aldehydes and sulfonyl hydrazides has been developed. Various epoxides...A simple and efficient method for the synthesis of pyrazoles through a silicotungstic acid (H_(4)SiW_(12)O_(40))-catalyzed cyclization of epoxides/aldehydes and sulfonyl hydrazides has been developed. Various epoxides/aldehydes were smoothly reacted with sulfonyl hydrazides to furnish regioselectivity 3,4-disubstituted 1H-pyrazoles. The application of such an earth-abundant, readily accessible, and nontoxic catalyst provides a green approach for the construction of 3,4-disubstituted 1H-pyrazoles. A plausible reaction mechanism has been proposed on the basis of control experiments, GC-MS and DFT calculations.展开更多
A novel reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides was performed in the presence of silver nitrate or triflate. Conjugated vinyl sulfones as dramatic products were obtained in moderate yield...A novel reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides was performed in the presence of silver nitrate or triflate. Conjugated vinyl sulfones as dramatic products were obtained in moderate yields and with Z-selectivity. A free radical mechanism has been proposed to account for the formation of the products.展开更多
A new and convenient visible-light-induced method has been developed for the synthesis of sulfonylated benzofurans via oxidative cyclization reaction of 1,6-enynes and arylsulfinic acids.This reaction was carried out ...A new and convenient visible-light-induced method has been developed for the synthesis of sulfonylated benzofurans via oxidative cyclization reaction of 1,6-enynes and arylsulfinic acids.This reaction was carried out under metal-free and mild conditions,in which the C-S,C-C and C=O bonds could be sequentially formed in one pot operation.展开更多
基金financial supports by the National Key R&D Program of China(Grant Nos.:2022YFC3400700 and 2022YFA0806400)the National Natural Science Foundation of China(Grant Nos.:22404027 and 31821002)Shanghai Municipal Science and Technology Major Project,China(Grant No.:2017SHZDZX01).
文摘Sulfonylation is extensively used to label DNA and RNA,assess their interactions,and quantify components including nucleobases and nucleosides/nucleotides although the sulfonylation sites remain controversial.Here,we systematically investigated the sulfonylation of adenine(ade)and its nucleosides/nucleotides with 5-(dimethylamino)-naphthalene-1-sulfonyl chloride(DNS-Cl),5-(diethylamino)-naphthalene-1-sulfonyl chloride(DEANS-Cl),and 5-((N,N-diethylleucyl)amino)-naphthalene-1-sulfonyl chloride(DELANS-Cl).Detailed spectral analysis with nuclear magnetic resonance(NMR)spectroscopy and high-resolution mass spectrometry(HRMS)showed similar sulfonylation behaviors among the reagents.For ade,its secondary amine in the imidazole ring(N9 H)sulfonylated more readily than the exocyclic amino group(N6 H2).For adenosine and its nucleotides,the 20-OH group in the ribosyl moiety was preferably sulfonylated,whereas the 30-OH was the preferred site for 20-deoxyadenosine and its nucleotides.Alkylation and amidation of the aromatic amino group in these 5-amino-naphthalene-1-sulfonyl chlorides did not influence the sulfonylation preferences.This offered a reliable approach and comprehensive details of such sites for ade and its nucleosides/nucleotides.
基金financial support from the Hunan Provincial Natural Science Foundation of China (No.2019JJ20008)
文摘An eco-friendly protocol for the synthesis of various 2-sulfonyl quinolines/pyridines through sulfonylation of heteroaromatic N-oxides with sodium sulfinates in water at ambient temperature under metal-and oxidant-free conditions has been developed.The mild reaction conditions,high reaction efficiency,operational simplicity,short reaction time and remarkable functional-group compatibility make the developed protocol very attractive for the preparation of 2-sulfonyl N-heteroaromatic compounds.
基金financial support from the National Natural Science Foundation of China(No.21761132021)Qin Lan Project from Jiangsu Province for J.Han。
文摘A visible-light-mediated reaction of indole derivatives employing arylsulfonyl chlorides as sulfonyl surrogates has been developed,which proceeds via the sequence of reduction of sulfonyl chloride,sulfonylation,and intramolecular cyclization.This mild protocol transforms a diverse array of indole tethered alkenes and simple sulfonyl chlorides into highly valuable functionalized tetrahydrocarbazoles in good yields.This reaction is also suitable for gram-scale synthesis,which provides an efficient and green access to multi-substituted tetrahydrocarbazoles.
基金financially supported by National Natural Science Foundation of China(No.21861019)Natural Science Foundation of Jiangxi Province(No.20202ACBL203006).
文摘The perfluoroalkylsulfonylation(CF_(3)SO_(2),C_(2)F_(5)SO_(2)and CHF_(2)SO_(2))in the enaminone C-H bonds has been developed simply via the promotion of molecular iodine by using stable and cheap sodium perfluoroalkyl sulfinates as coupling partners.The stereoselective synthesis of E-configuratedα-perfluoroalkylsulfonyl enaminones has been realized via unprecedented C-H bond elaboration and C=C double bond configuration inversion by free radical process.
文摘The development of practical methods for the direct and selective C(sp^(3))‒H functionalization of hydrocarbons is an attractive topic in synthetic chemistry.Although the radical‐mediated hydrogen atom transfer(HAT)process has shown considerable potential in such reactions,it still faces fundamental problems associated with reactivity and selectivity.Herein,we report a convenient and economic approach to site‐selective C(sp^(3))‒H sulfonylation via photo‐induced HAT catalysis.Employing a conjugated polycyclic quinone as a direct HAT photocatalyst,commercially available inorganic sulfinates as the sulfonylation source,copper triflate as an inexpensive oxidant,a variety of toluene derivatives and cycloalkanes were converted into biologically and synthetically interesting sulfone products under mild conditions.The mechanistic studies reveal that the reaction sequence involves direct HAT‐induced radical formation and a subsequent copper‐mediated organometallic process for the C‒S bond formation.This method offers an appealing opportunity to furnish high value‐added products from abundant hydrocarbon starting materials and inexpensive reagents.
文摘A new and convenient procedure is developed for the preparation of N-sulfonylbenzotriazoles from sodium sulfinates and benzotriazoles using molecular iodine as catalyst via the S-N bond formation reaction. This catalytic radical sulfonylation proceeds efficiently in air at room temperature under neutral conditions, and in short reaction time, to afford the corresponding N-sulfonylbenzotriazoles in good yields, thus extending the catalytic application of molecular iodine in organic synthesis.
基金supported by the International Cooperation Project of Qinghai Province(No.2018-HZ-806)the Youth Innovation and Technology Project of Higher School in Shandong Province(No.2019KJC021)+3 种基金the Natural Science Foundation of Shandong Province(No.ZR2018MB009)the Qinghai Key Laboratory of Tibetan Medicine Research(No.2017ZJ-Y11)CAS“Light of West China”Program 2018Entrepreneurship Training Program for College Students(No.201910049)。
文摘A convenient and regioselective sulfonylation/cyclization of 1,6-enynes with arylazo sulfones has been developed to access a series of sulfonylated γ-butyrolactams.The present reaction could be efficiently conducted under catalyst-and additive-free conditions,in which C-S and C-C bonds were selectively constructed in one-pot procedure.
基金supported by the National Natural Science Foundation of China(22171206)the Natural Science Foundation of Zhejiang Province(LZ23B020001)the Zhejiang Provincial Ten Thousand Talent Program(2023R5244)。
文摘Enantioselective intramolecular radical difunctionalization of alkenes involving sulfur dioxide through a three-component reaction of 4-arylpent-4-enoic acids,sodium hydrogen sulfite and thianthrenium salts under copper catalysis and photocatalysis is reported,allowing the construction of chiral 5-((sulfonyl)methyl)dihydrofuran-2(3H)-ones with β-quaternary stereocenters.During the transformation,sodium hydrogen sulfite is used as the sulfur dioxide surrogate.Excellent enantiocontrol(up to 99%ee)and wide functional group compatibility are observed in this asymmetric radical sulfonylation.
基金the National Natural Science Foundation of China(No.21971071)the Natural Science Foundation of Guangdong Province(No.2021A1515010155)the Fundamental Research Funds for the Central Universities(No.2020ZYGXZR075).
文摘By employing a readily available CuCI/DDQ catalyst system,we herein report a direct C(sp^(3))-H sulfonylation of xanthene derivates with odorless sodium sulfinates.Various 9H-xanthenes,thioxanthenes,and 9,10-dihydroacridines are efficiently transformed into the desired benzylic sulfonyl products via a radical/radical cross-coupling process,proceeding with the merits of broad substrate scope,operational simplicity,good functional group compatibility,and mild reaction conditions.
基金supported by a Start-up Grant from Guangdong Pharmaceutical University(Grant Nos.51361303,51361304)the Youth Talent Support Programme of Guangdong Provincial Association for Science and Technology(SKXRC202303).
文摘Comprehensive Summary The selective oxidative sulfonylation of alkenes with selenium sulfonate depended on the reaction conditions.The electrochemical C—H sulfonylation proceeded smoothly to afford(E)-vinyl sulfones with good selectivity in an undivided cell without external oxidant.While aerobic trifunctionalization of alkenes occurred in the presence of KI in the air,which providesβ-keto selenosulfones via the formation of C—O,C—S,and C—Se bonds in one-pot.Following control experiments,a plausible mechanism is proposed to rationalize the experimental results.
基金National Natural Science Foundation of China(Nos.22178315,22378363,22078298 and 21978271)the Natural Science Foundation of Zhejiang Province of China(No.LY21B020007)+1 种基金China Postdoctoral Science Foundation(No.2022M712824)Key Research and Development Program of Zhejiang Province(No.2022C03169)for financial support.
文摘Herein, we reported an efficient and straightforward method to realize desaturated β-C(sp^(3))-H sulfonylation andphosphonylation of cyclic amines driven by electrochemistry using catalytic amounts of CP_(2)Fe as the redoxmediator. This protocol which had good functional group compatibility, provided the desired enaminyl sulfoneand enaminyl phosphine oxide products with high chemo- and regio-selectivity under mild conditions. Severalmechanistic studies have suggested that cyclic amines underwent multiple single-electron oxidation and deprotonation processes, followed by a capture step involving either a sulfonyl radical or a phosphonyl radical, ultimately leading to the desired products.
基金We gratefully acknowledge the financial support from the National Natural Science Foundation of China(22101059)the Research Program of Young Teachers in Universities of Guangxi(2021KY0057)the Central Government Guides Local Science and Technology Development Fund Projects(guide ZY21195014)and Guangxi Normal University.
文摘Tunable photoredox-catalyzed chlorosulfonylation and oxysulfonylation ofα-trifluoromethylstyrenes with sulfonyl chloride were facilely achieved by simply manipulating the photocatalyst and solvent.This strategy makes full use of the structural features of sulfonyl chloride to afford diverse bifunctional products ofα-trifluoromethylstyrenes in up to 95%yield with excellent functional group tolerance.
基金supported by the National Natural Science Foundation of China(22471073,22171087)the Technology Innovation Project of Shanghai Municipal Agricultural Committee(HNK(T2023302))+2 种基金the Innovation Program of Shanghai Municipal Education Commission(2023ZKZD37)the Ministry of Education(PCSIRT)the Fundamental Research Funds for the Central Universities。
文摘Organosilanes are not found in nature but play a crucial role in the sustainable development of modern society.Si-chiral organosilanes represent a type of novel chemical space that is highly desirable for research oriented in terms of their properties,including synthetic chemistry,drug discovery,and materials and life sciences.While much effort has been given to the catalytic enantioselective construction of Si-chirality,the facile synthesis of multifunctional Si-chiral silanes remains undeveloped.Here,we report an unprecedented highly enantioselective copper-catalyzed desymmetric sulfonylation or acylation of prochiral 1,3-siladiols for the expedient synthesis of multifunctional Si-chiral silanes with both a hydroxymethyl group and an ester group as synthetic handles.A one-pot tandem desymmetric sulfonylation/substitution sequence,internally reusing waste chloride or bromide formed from the upstream sulfonylation step as the reagent for a substitution step,is also exploited for the atom-efficient synthesis of Si-chiral silylmethanols featuring a chloromethyl or bromomethyl group.A newly developed sterically confined pyridine-bis(oxazoline)(PYBOX)ligand with a bulky C4 amide-containing shielding group is crucial for achieving excellent reactivity and enantioselectivity.The scale-up synthesis and various diversifying elaborations of multifunctional Si-chiral silylmethanols further highlight the synthetic practicability of this protocol.
基金supported by the Youth Innovation Technology Project of Higher School in Shandong Province(No.2019KJC021)Qinghai Science and Technology Achievement Transformation Project(No.2019-SF-122)Qinghai Key Laboratory of Tibetan Medicine Research(No.2021-ZJ-Y03)。
文摘Sulfur-containing organic compounds display wide applications in the field of materials science,synthetic chemistry,and pharmaceutical industry.Thus,numerous synthetic strategies have been developed for the synthesis of sulfur-containing compounds in synthetic chemistry.In recent years,the utilization of sulfinic acids as versatile synthons has emerged as attractive and powerful approach to access various organosulfur compounds through sulfonylation,sulfinylation or sulfenylation reactions.In this review,we summarized the recent progress in the construction of various sulfur-containing compounds from sulfininc acids.Selected examples of substrates and the related reaction mechanisms are described here.This review intends to provide readers a comprehensive understanding on the synthesis of sulfur-containing molecules from sulfinic acids and provide help for future synthetic research.
基金the National Natural Science Foundation of China(Nos.21971138 and 21472107)。
文摘N,N’-Disulfonylhydrazines have been proven to be the most reactive precursors of the sulfonyl radicals among all types of sulfonyl substituted hydrazines as early as half a century ago.However,the sulfonyl radicals generated from these compounds have not been used in organic synthesis except the simple selfdimerization synthesis of disulfones controlled by the"solvent-cage-effects".In this article,N,N’-disulfonylhydrazines were introduced as new sulfonylating reagents and their combinations with NIS were disclosed as new iodosulfonylating reagents of allcynes.Finally,a highly efficient method for the synthesis of(E)-β-iodovinyl arenesulfones was developed by mixing an alkyne,a N,N’-disulfonylhydrazine and NIS in aqueous THF at room temperature for 5 min.
文摘Several bis（trifluoromethylsulfonyl）phenylamines have been synthesized and used as internal donors for the preparation of heterogeneous Ziegler-Natta catalysts for propylene polymerization. These new cata- lysts are highly active and stereospecific in combination with an external donor for the polymerization of propylene. The activity of these catalysts is dramatically influenced by the electronic capability of the phenyl substituents on the sulfonyl phenylamines. Therefore, the performances of the catalysts can be modified by adjusting the electronic property of the phenyl substituents of the sulfonyl phenylamines.
基金financially supported by the National 863 Program(No.2007AA03Z226)the National Key Program for Basic Research of China(No.2002CB211800 and 2009CB220100).
文摘Composite polymer electrolytes based on mixing soft-segment waterborne polyurethane （WPU） and 1-butyl-3-methylimidazolium bis[（trifluoromethyl）sulfonyl]imide （BMImTFSI） have been prepared and characterized. The addition of BMImTFSI results in an increase of the ionic conductivity. At high BMImTFSI concentration （BMImTFSI/WPU = 3 in weight ratio）, the ionic conductivity reaches 4.27 × 10^-3 S/cm at 30 ℃. These composite polymer electrolytes exhibit good thermal and electrochemical stability, which are high enough to be applied in lithium batteries.
基金financially supported by the National Natural Science Foundation of China (Nos. 22001034 and 21804019)the Open Fund of the Jiangxi Province Key Laboratory of Synthetic Chemistry (No. JXSC202008)the Research Found of East China University of Technology (Nos. DHBK2019264, DHBK2019265 and DHBK2019267)。
文摘A simple and efficient method for the synthesis of pyrazoles through a silicotungstic acid (H_(4)SiW_(12)O_(40))-catalyzed cyclization of epoxides/aldehydes and sulfonyl hydrazides has been developed. Various epoxides/aldehydes were smoothly reacted with sulfonyl hydrazides to furnish regioselectivity 3,4-disubstituted 1H-pyrazoles. The application of such an earth-abundant, readily accessible, and nontoxic catalyst provides a green approach for the construction of 3,4-disubstituted 1H-pyrazoles. A plausible reaction mechanism has been proposed on the basis of control experiments, GC-MS and DFT calculations.
文摘A novel reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides was performed in the presence of silver nitrate or triflate. Conjugated vinyl sulfones as dramatic products were obtained in moderate yields and with Z-selectivity. A free radical mechanism has been proposed to account for the formation of the products.
基金supported by the Natural Science Foundation of Shandong Province (No. ZR2018MB009)the International Cooperation Project of Qinghai Province (No. 2018-HZ-806)+1 种基金the Qinghai Key Laboratory of Tibetan Medicine Research (No. 2017-ZJ-Y11)the National Natural Science Foundation of China (No. 21302109)
文摘A new and convenient visible-light-induced method has been developed for the synthesis of sulfonylated benzofurans via oxidative cyclization reaction of 1,6-enynes and arylsulfinic acids.This reaction was carried out under metal-free and mild conditions,in which the C-S,C-C and C=O bonds could be sequentially formed in one pot operation.
