Photocatalyzed site‐selective C(sp^(3))‒H sulfonylation of toluene derivatives and cycloalkanes with inorganic sulfinates

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.

Controllable Construction of Vinyl Sulfones and β-Keto Selenosulfones via Selective Oxidative Sulfonylation of Alkenes

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.

TsCl-promoted sulfonylation of quinoline N-oxides with sodium sulfinates in water

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.

Direct C(sp^(3))-H Sulfonylation of Xanthene Derivatives with Sodium Sulfinates by Oxidative Copper Catalysis

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.

Visible-light-irradiated tandem sulfonylation/cyclization of indole tethered alkenes for the synthesis of tetrahydrocarbazoles

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.

Metal-free C(sp^(2))-H perfluoroalkylsulfonylation and configuration inversion:Stereoselective synthesis ofα-perfluoroalkylsulfonyl E-enaminones

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.

An Efficient Method for Sulfonylation of Amines, Alcohols and Phenols with N-Fluorobenzenesulfonimide Under Mild Conditions

A new and convenient procedure was developed for the preparation of sulfonamides and sulfonic esters using N-fluorobenzenesulfonimide（NFSI） as a novel phenylsulfonyl group transfer reagent. In this protocol, a broad range of functional groups were tolerated to give the corresponding sulfonamides or sulfonic esters in moderate to excellent yields. The synthetic strategy for sulfonamides formation proceeded efficiently even under base-, metal- and additive-free conditions with the advantages of operational simplicity, mild reaction conditions as well as short reaction time.

Iodine-catalyzed N-sulfonylation of benzotriazoles with sodium sulfinates under mild conditions

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.

Catalyst-and additive-free selective sulfonylation/cyclization of 1,6-enynes with arylazo sulfones leading to sulfonylated γ-butyrolactams

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.

Tunable photocatalytic oxysulfonylation and chlorosulfonylation ofα-CF_(3) alkenes with sulfonyl chlorides

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.

Bis(trifluoromethylsulfonyl)phenylamines as Internal Donors for Ziegler-Natta Polymerization Catalysts

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.

Synthesis and characterization of mixing soft-segmented waterborne polyurethane polymer electrolyte with room temperature ionic liquid

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.

Sulfonyl Imidazoles as Reagents for the Preparation of Sulfonates and Sulfonamides

Several new sulfonates and sulfonamides were synthesized with sulfonyl imidazoles as reagents. These compounds were characterized by ^1H NMR. The melting points of all solids synthesized were obtained on Fisher-Johns Melting Point Apparatus.

A Facile Synthesis of 3,5-Diaryl 1,2,4-Selenadiazoles from Aryl Selenoamides

A facile synthesis of 3,5-diaryl 1,2,4-selenadiazoles was provided by treatment of aryl selenoamides with p-methylphenyl sulfonyl chloride in chloroform.

Bioisostere of Sulfonyl Moiety-The Synthesis of New ALS Inhibitors N-(Asymmetry Disubstituted Phosphoryl)-N'-(4,6-dimethoxypyrimidin-2-yl) Ureas

In view of the isosterism of the sulfonyl (-SO2-) and phosphoryl groups [-P(O)(OR)-,R=H, CH3, C2H5, etc], two new types of ureas, N-(N-aryl-O-alkyl phosphoryl)-N'-(4, 6-dimethoxypyrinddin-2-yl) ureas 2 and N-(N-aryl-N-alkyl phosphoryl)-N'-(4, 6-dimethoxy pyrimidin-2-yl)ureas 3, were synthesized by treating N- (arylandnochlorophosphoryl ) - N'- (4, 6-dimethoxypyriAndinyl-2-) ureas 4 with alcohols or amines. Compounds 4 were obtained by reactingdichlorophosphoryl isocyanate with 4,6 - di meth oxy- 2-aminopyrimidine, and then with aromaticamines. The enzyme tests (in vitro) indicated that compounds 2 and 3 were two novel classes ofacetolactate synthase (ALS) inhibitors, which showed that the phosphoryl group, [-P(O)(OR)-], or[-P(O)(NHR)-], was a good bioisostere of the sulfonyl group (-SO2-) in sulfonylurea.

Chiral Separation of Ibuprofen and Terbutaline by Nonaqueous Capillary Electrophoresis with Conductance Detection

In the nonaqueous N,N -dimethylformamide medium, the chiral drugs ibuprofen and terbutaline were successfully separated with sulfonyl- β -cyclodextrin(s- β -CD) as the chiral selector by capillary electrophoresis with conductance detection. The comparison of the effects of three CDS( β -CD, diethylic- β -CD, sulfonyl- β -CD) on the chiral separation was made and the resolution mechanism was proposed.

One-Pot Reaction of Aldehydes,α-Haloketones and (Phenylsulfonyl)acetonitrile Promoted by SmI3

One-pot reaction of aldehydes, ?haloketones and (phenylsulfonyl)acetonitrile promoted by SmI3 proceeded smoothly to give 1-cyano-1-phenylsulfonyl-2-aryl-3-aroyl-propane derivatives in moderate to good yields.

Studies on Artificial Imitation of Glutathione Peroxidase by Chemical Mutation

fter the alcoholic group of serine located in the binding site of Anti-HumanIgM(Fcμ) (Rabbit IgG) was selectively activated by phenylmethylsulfonyl fluoride(PMSF) and displaced with hydrogen selenide(H2Se) , the serine residue was con-verted to selenocysteine(SeCys). Because SeCys is a catalytic group of glutathioneperoxidase (GPX), the mutated antibody has the GPX activity which is seventytimes more than that of PZ51, the best GPX mimic in the world. Moreover, themutated antibody remains its original antibody titer.

Low-valent Titanium Induced Reductive Coupling Reaction of Aryl Sulfonyl Chlorides with α,β-Unsaturated Esters

The reductive coupling reactions of aryl sulfonyl chloride induced by (TiCl4-Zn) reagent affords diaryl disulfide. However, reaction of aryl sulfonyl chloride with α,β-unsaturated ester under the same condition affords β-arylsulfo ester.