Synthesis Of Sulfonamides Research Articles

I2/TBHP Mediated C-N and C-H Bond Cleavage of Tertiary Amines toward Selective Synthesis of Sulfonamides and β-Arylsulfonyl Enamines: The Solvent Effect on Reaction.

A novel method toward synthesis of sulfonamides and β-arylsulfonyl enamines has been developed via I2/TBHP mediated C-N and C-H bond cleavage of tertiary amines, which features highly selective formation of two different target products depending on the reaction solvent. The experimental results reveal that H2O as the solvent could effectively achieve the C-N bond cleavage to produce sulfonamides due to H2O participating in the reaction process where H2O plays a dual role. Differing from H2O, organic solvents (such as dimethyl sulfoxide) could promote the C-H bond cleavage of tertiary amines to yield β-arylsulfonyl enamines.

ChemInform Abstract: Palladium‐Catalyzed Site‐Selective C—H Functionalization of Weakly Coordinating Sulfonamides: Synthesis of Biaryl Sulfonamides.

AbstractUnsubstituted aromatic sulfonamides are treated with aryl iodides under optimized conditions A).

ChemInform Abstract: Metal‐Free Synthesis of Sulfonamides via Iodine‐Catalyzed Oxidative Coupling of Sulfonyl Hydrazides and Amines.

Abstract A novel, rapid, and environmentally-friendly protocol for the synthesis of sulfonamides using iodine as catalyst under solvent-free conditions is described. This method involves the oxidative coupling of sulfonyl hydrazides and amines in the presence of catalytic amount of iodine using TBHP as oxidant. This protocol does not require purification techniques such as column chromatography and recrystalization.

Electrochemical Oxidative Amination of Sodium Sulfinates: Synthesis of Sulfonamides Mediated by NH4I as a Redox Catalyst.

An efficient protocol for the synthesis of sulfonamides via the electrochemical oxidative amination of sodium sulfinates has been developed. The chemistry proceeds in a simple undivided cell employing a substoichiometric amount of NH4I that serves both as a redox catalyst and a supporting electrolyte; in this manner additional conducting salt is not required. A wide range of substrates, including aliphatic or aromatic secondary and primary amines, as well as aqueous ammonia, proved to be compatible with the protocol. Scale-up was possible, thereby demonstrating the practicality of the approach. The electrolytic process avoids the utilization of external oxidants or corrosive molecular iodine and therefore represents an environmentally benign means by which to achieve the transformation.

ChemInform Abstract: Sustainable Synthesis of Sulfonamides Using Supported Ionic Liquid Phase Catalyst Containing Keggin‐Type Anion.

A silica-supported ionic liquid phase catalyst containing Keggin-type anion has been prepared by covalent grafting of ferrocene-tagged ionic liquid in a matrix of silica followed by anion metathesis reaction. This novel catalyst served as a robust heterogeneous catalyst for the synthesis of biologically active sulfonamides from 4-toluenesulfonyl chloride and amines. Additionally, recycling experiments showed that the catalyst could be reused five times. Copyright © 2015 John Wiley & Sons, Ltd.

ChemInform Abstract: Iodine‐Catalyzed Expeditious Synthesis of Sulfonamides from Sulfonyl Hydrazides and Amines.

AbstractA new protocol for the synthesis of sulfonamides via an iodine‐catalyzed sulfonylation of amines with sulfonyl hydrazides is developed.

Sulfonyl Azides as Precursors in Ligand-Free Palladium-Catalyzed Synthesis of Sulfonyl Carbamates and Sulfonyl Ureas and Synthesis of Sulfonamides.

An efficient synthesis of sulfonyl carbamates and sulfonyl ureas from sulfonyl azides employing a palladium-catalyzed carbonylation protocol has been developed. Using a two-chamber system, sulfonyl azides, PdCl2, and CO gas, released ex situ from Mo(CO)6, were assembled to generate sulfonyl isocyanates in situ, and alcohols and aryl amines were exploited as nucleophiles to afford a broad range of sulfonyl carbamates and sulfonyl ureas. A protocol for the direct formation of substituted sulfonamides from sulfonyl azides and amines via nucleophilic substitution was also developed.

Metal-free synthesis of sulfonamides via iodine-catalyzed oxidative coupling of sulfonyl hydrazides and amines

A novel, rapid, and environmentally-friendly protocol for the synthesis of sulfonamides using iodine as catalyst under solvent-free conditions is described. This method involves the oxidative coupling of sulfonyl hydrazides and amines in the presence of catalytic amount of iodine using TBHP as oxidant. This protocol does not require purification techniques such as column chromatography and recrystalization.

Synthesis of benzothiazine sulfonamides via heteroatomic Diels–Alder reaction of para-fluoro-N-sulfinylaniline with bicyclo[2.2.1]heptenes

Reaction of 4-fluoro-N-sulfinylaniline with norbornene and norbornadiene has afforded the Diels–Alder adducts of benzothiazine structure that have been oxidized into the corresponding benzothiazine sulfonamides. Structure of the obtained compounds and stereochemistry of the diene addition and epoxidation of norbornene olefin bonds have established by means of X-ray diffraction method.

Palladium-Catalyzed Site-Selective C-H Functionalization of Weakly Coordinating Sulfonamides: Synthesis of Biaryl Sulfonamides.

A novel and site selective C-H functionalization of unsubstituted sulfonamides has been developed for the synthesis of ortho aryl sulfonamides. The reaction involves highly regioselective ortho mono arylation of weakly coordinating SO2 NH2 directing group by means of aryl iodides. Palladium acetate in the presence of silver(I) oxide is found to be the most effective catalytic system.

Synthesis of novel sulfonamides under mild conditions with effective inhibitory activity against the carbonic anhydrase isoforms I and II

Novel sulfonamide derivatives 6a–i, as new carbonic anhydrase inhibitors which candidate for glaucoma treatment, were synthesized from the reactions of 4-amino-N-(4-sulfamoylphenyl) benzamide 4 and sulfonyl chloride derivatives 5a–i with high yield (71–90%). The structures of these compounds were confirmed by using spectral analysis (FT-IR, 1H NMR, 13C NMR, LC/MS and HRMS). The inhibition effects of 6a–i on the hydratase and esterase activities of human carbonic anhydrase isoenzymes, hCA I and II, which were purified from human erythrocytes with Sepharose®4B-l-tyrosine-p-aminobenzene sulfonamide affinity chromatography, were studied as in vitro, and IC50 and Ki values were determined. The results show that newly synthesized compounds have quite powerful inhibitory properties.

One-Step Synthesis of Sulfonamides from N-Tosylhydrazones.

The first described reaction between N-tosylhydrazone and SO2 is reported to provide alkyl sulfonamides in the presence of various amines. In this procedurally simple method, hydrazones of both unsaturated aldehydes and ketones proceed in moderate to excellent yields. Primary and secondary aliphatic amines are accommodated in this reaction, which provides a novel route to sulfonamides.

Palladium nanoparticles as reusable catalyst for the synthesis of N-aryl sulfonamides under mild reaction conditions

An efficient palladium nanoparticles-catalyzed N-arylation of sulfonamides and sulfonyl azides is described. This procedure serves as an active protocol for intermolecular C–N bond formation using Pd(OAc)2 in PEG-400 under air. Aryl bromides and triflates react at 35°C, while aryl chlorides require heating to 50°C and give the desired products only in low yields. This reaction proceeds smoothly in acceptable yields using low catalyst loading.

A general iodine-mediated synthesis of primary sulfonamides from thiols and aqueous ammonia.

A general and efficient methodology for preparing primary sulfonamides has been developed. In the presence of iodine as the catalyst and TBHP (70% in water) as the oxidant, a wide range of primary sulfonamides were prepared from the corresponding thiols and aqueous ammonia in moderate to good yields.

Iodine-catalyzed expeditious synthesis of sulfonamides from sulfonyl hydrazides and amines.

A new synthesis of sulfonamides has been developed via an iodine-catalyzed sulfonylation of amines with arylsulfonyl hydrazides. This metal-free strategy employs readily accessible and easy to handle starting materials, catalysts and oxidants, and can be easily conducted under mild conditions, providing a convenient access to a wide range of sulfonamides in moderate to excellent yields within a short reaction time.

Synthesis of sulfonamides via copper-catalyzed oxidative C-N bond cleavage of tertiary amines.

A copper-catalyzed coupling reaction of sulfonyl chlorides with tertiary amines via the oxidative C-N bond cleavage of tertiary amines was developed. Sulfonamides were synthesized using this strategy in moderate to good yields. The reaction was applicable to various tertiary amines, as well as sulfonyl chlorides.

ChemInform Abstract: The Synthesis of Alkyl and (Hetero)aryl Sulfonamides from Sulfamoyl Inner Salts.

AbstractZwitterionic inner salts of type (I) readily react with organometallic reagents under mild conditions to give N‐sulfonyl‐substituted urethanes in moderate yields.

Synthesis of cyclic sulfonamides by reaction of N-sulfinyl-3-(trifluoromethyl)aniline with norbornenes

N-Sulfinyl-3-(trifluoromethyl)aniline reacted with bicyclo[2.2.1]hept-2-ene and bicyclo[2.2.1]-hepta-2,5-diene to give the corresponding Diels‒Alder adducts which were oxidized to 8-trifluoromethyl-2,3,4,4a,6,10b-hexahydro-5λ 6-1,4-methanodibenzo[c,e][1,2]thiazine-5,5(1H)-diones. The cycloaddition occurred predominantly with participation of the S=N–C1=C6 fragment of N-sulfinyl-3-(trifluoromethyl)aniline and exclusively at the endo side of bicyclo[2.2.1]heptenes.

3-Component synthesis of α-substituted sulfonamides via Brønsted acid-catalyzed C(sp(3))-H bond functionalization of 2-alkylazaarenes.

A Brønsted acid-catalyzed addition of 2-alkylazaarenes to in situ generated N-sulfonylimines through selective C(sp(3))-H bond functionalization has been developed. This protocol provides an atom- and step-economic approach to α-substituted sulfonamides.

Selective Access to Heterocyclic Sulfonamides and Sulfonyl Fluorides via a Parallel Medicinal Chemistry Enabled Method.

A sulfur-functionalized aminoacrolein derivative is used for the efficient and selective synthesis of heterocyclic sulfonyl chlorides, sulfonyl fluorides, and sulfonamides. The development of a 3-step parallel medicinal chemistry (PMC) protocol for the synthesis of pyrazole-4-sulfonamides effectively demonstrates the utility of this reagent. This reactivity was expanded to provide rapid access to other heterocyclic sulfonyl fluorides, including pyrimidines and pyridines, whose corresponding sulfonyl chlorides lack suitable chemical stability.