Bromodimethylsulfonium Bromide Research Articles

Optimization of Catalytic Bromination of Acetophenones Using Taguchi's Method

AbstractA new, efficient and environmental benign one‐pot protocol for the synthesis of α‐bromoacetophenones has been designed via the regioselective monobromination of aromatic carbonyl compounds with Bromodimethylsulfonium Bromide (BDMS) in catalytic environment of MgO nanoparticles and products were obtained in moderate to superior yields. Structure of synthesized compounds were elucidated by their 1H and 13C NMR spectroscopy, further Taguchi based optimization is utilized to maximize the product yield using L27 Orthogonal Array (OA) constructed by five control factors including acetophenones (AP), BDMS, Temperature, Time and MgO with their three levels. The optimal level of AP, BDMS, Temperature, Time and MgO are found up to 1.0 mmol, 2.0 mmol, 60 °C, 50 Min and 10 mol%, respectively.

Halogenation of arenes with sulfoxide and oxalyl halide

The utilization of DMSO or Ph2SO/(COBr)2 or (COCl)2 for the bromination or chlorination of arenes has been explored. Notably, monobromination of activated arenes can be achieved with high regioselectivity using the combination of dimethyl sulfoxide and oxalyl bromide. Bromodimethylsulfonium bromide generated in situ was proposed to be the active species for bromination. In contrast, the practicality of chlorination of arenes with DMSO or Ph2SO/(COCl)2 is limited due to production of the formation of by-products such as aryldimethylsulfonium chlorides or dichlorinated arenes.

Practical synthesis of unsymmetrical disulfides promoted by bromodimethylsulfonium bromide.

Oxidative cross-coupling of two thiols is the most direct tool for the synthesis of unsymmetrical disulfides and highly desirable across academia and industry. However, the inevitable formation of significant amounts of the corresponding symmetrical by-products is a major issue. We herein present a method toward the synthesis of unsymmetrical disulfides in which the homo-coupling of the thiols is effectively inhibited by adding the two thiols sequentially, taking advantage of rapid oxidation of the thiol by bromodimethylsulfonium bromide.

1,2-Fluorosulfenylation of unactivated alkenes with thiols and a fluoride source promoted by bromodimethylsulfonium bromide.

A practical method that enables the fluorosulfenylation of unactivated alkenes processed directly with thiols and fluoride salts is presented. Good to excellent efficiencies and functional group tolerance are observed for both alkene substrates and thiols. The procedure also allows the use of gaseous ethylene as a two-carbon building block for β-fluoro thioether products.

The Role of (BDMS) Bromodimethylsulfonium bromide as a Catalyst and Brominating Reagent: A Concise Overview

AbstractBromodimethylsulfonium bromide (BDMS) is an expedient storage of molecular bromine or bromine radicals or bromonium ions and also of nucleophilic bromide ion. It is an easily available, inexpensive and versatile reagent. It is used as an effective brominating reagent as well as a valuable catalyst for several organic conversions. The prominent characteristics of this compound are the straight forwardness of the process, the ease of access of the compound, no requirement of chromatographic separation, no additional base, Lewis acid, or any other catalyst, better yields in comparatively less reaction times and assist to maintain the stoichiometric ratio during the reactions. The present article includes the catalytic applications as well as its brominating role in organic reactions.

Facile methylthiomethylation of the carboxylic acid with bromodimethylsulfonium bromide

Herein, a mild and simple method to synthesize methylthiomethyl (MTM) esters with commercially available bromodimethylsulfonium bromide is described. The developed procedure allows the methylthiomethylation of a vast scope of carboxylic acids, including alkyl, (hetero)aryl and unsaturated acids, with the tolerance of various functionalities. Several drug or bioactive molecules and amino acids have been successfully converted to their MTM ester analogues as well.

A continuous flow bromodimethylsulfonium bromide generator: application to the synthesis of 2-arylaziridines from styrenes

A continuous flow procedure for the synthesis of aziridines from alkenes based on the in situ generation and utilization of bromodimethylsulfonium bromide (BDMS) is presented. In this process, BDMS was generated from hydrogen bromide and dimethylsulfoxide in the presence of the olefin, ensuing the corresponding 1,2-bromodimethylsulfonium bromide addition product. The solution containing this intermediate was mixed with a primary amine in flow, resulting in a rapid aziridination in a fast 3-step telescoped process. Notably, the exothermic formation of BDMS could be readily controlled in flow mode at room temperature, rendering a safe and reliable process. The complete sequence only required 7 min of total residence time, and provided a variety of 2-aryl aziridines in synthetically useful yields.

Bromodimethylsulfonium bromide: A novel reagent for the one pot synthesis of potent Nα-ureido peptides and study of molecular docking and antibacterial activities

Nα-protected ureidopeptides were synthesized efficiently using Bromodimethylsulfonium bromide mediated Curtius rearrangement through the in-situ generation of carboxylated sulfonium intermediate. Conversion of carboxylic acids to ureidopeptides in good yield was obtained in one-pot under mild reaction conditions, through a simple workup. To check the binding modes and binding affinity of urea functional group with target protein, the synthesized compounds were subjected to docking studies. Docking scores confirm that the molecules Boc-Leu-ψ[NHCONH]-Ala-OMe and Leu-ψ[NHCONH]-Ala-OMe have least energy and good agreement with the results of antibacterial studies against Escherichia coli, Staphylococcus aureus and Pseudomonas aeroginosa with respect to Streptomycin sulphate as a standard. The synthesized compounds were well characterized by IR, 1H NMR, 13C NMR and mass spectral studies.

Metal-Free Oxidative C(sp3)–N Coupling by HBr and DMSO: A Novel Synthesis of 2,3-Dihydroquinazolin-4(1H)-ones

A metal-free oxidative C(sp3)–N coupling process has been developed for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones. The reaction between primary amines, isatoic anhydride, and benzylic alcohols in the presence of HBr in DMSO at 80 °C affords 2,3-dihydroquinazolin-4(1H)-ones in excellent yields. Under these reaction conditions, benzylic alcohols react with in situ generated bromodimethylsulfonium bromide to form alkoxysulfonium intermediates. These intermediates undergo an oxidative cyclization reaction with primary amines and isatoic anhydride to produce the title products.

Synthesis of Difurylarylmethanes Catalyzed by Bromodimethylsulfonium Bromide

Synthesis of Difurylarylmethanes Catalyzed by Bromodimethylsulfonium Bromide

Solvent-free one-pot synthesis of polysubstituted tetrahydropyrimidines and their antioxidant and antimicrobial properties

A versatile and highly efficient one-pot multicomponent approach for the synthesis of novel multisubstituted tetrahydropyrimidine (dimethyl/diethyl-1,3-disubstituted-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylate) derivatives catalyzed by Bromo(dimethylsulfonium) bromide under solvent-free conditions has been developed. The protocol is eco-friendly, operationally simple, and proceeds in short reaction time, providing high-yield, high-purity (90–95 %) stable target compounds without any side products. Further, the scope of this protocol extended to aliphatic substrates, thus establishing the versatility of the catalyst. The lead compounds were screened for antioxidant and antimicrobial activities. Among them, compounds 4a, 4d, 4e, 4j exhibited excellent antibacterial activity when compared with the standard gentamycin. Compounds 4e and 4k exhibited excellent antifungal activity in comparison with the standard itraconazole. The results of this study revealed that all synthesized compounds were significantly scavenged DPPH free radicals in a concentration-dependent manner. The IC50 values of the compounds is between 13.28 and 23.16 µM when compared with the standard ascorbic acid. Compound 4f was found to be a good antioxidant. The synthesis of polysubstituted tetrahydropyrimidines (dimethyl/diethyl-1,3-disubstituted-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylate) derivatives from but-2-ynedioates, amines, and formaldehyde via a one-pot multicomponent reaction is reported. The reactions were performed under solvent-free and mild conditions with shorter reaction times, high purity, and high yield. The obtained products are interesting heterocyclic compounds containing ester functional groups and exhibited excellent antibacterial activity and moderate-to-good antioxidant properties.

Bromodimethylsulfonium bromide: an efficient catalyst for one-pot synthesis of 4-phenacylidene flavene derivatives

The synthesis of 4-phenacylidene flavenes (3) was accomplished by a one-pot pseudo three-component condensation reaction between salicylaldehydes and acetophenones in the presence of 20mol% of bromodimethylsulfonium bromide (BDMS) in acetonitrile at room temperature. The attractive features of this protocol are: use of organo-catalyst BDMS, simple reaction procedure, high bond-forming efficiency, good yields, and environmentally benign reaction conditions.

A direct approach for the expedient synthesis of unsymmetrical ethers by employing bromodimethylsulfonium bromide (BDMS) mediated C–S bond cleavage of naphthalene-2-ol sulfides

Synthesis of unsymmetrical ether derivatives using 1-(aryl(alkyl/arylthio)methyl)-naphthalene-2-ol and alcohols in the presence of bromodimethylsulfonium bromide (BDMS).

A General and Efficient Method for the Formylation of Amines Catalyzed by Bromodimethylsulfonium Bromide

A General and Efficient Method for the Formylation of Amines Catalyzed by Bromodimethylsulfonium Bromide

ChemInform Abstract: Bromodimethylsulfonium Bromide (BDMS)‐Catalyzed Synthesis of Substituted Pyrroles Through a One‐Pot Four‐Component Reaction.

AbstractA great variety of pyrroles [(V), (VIII), and (X)] is conveniently and ecofriendly synthesized.

Efficient bromination of polyaniline base to poly(2-bromoaniline)-bromide salt and its application as a recyclable catalyst for the synthesis of 2-methyl-4-anilino-1,2,3,4-tetrahydroquinolines

Efficient bromination of polyaniline base to poly(2-bromoaniline)-bromide is successfully carried out using bromodimethylsulfonium bromide. Poly(2-bromoaniline)-bromide salt was obtained in a dry amorphous nature, having high conductivity (2.5S/cm) with agglomerated spherical morphology. Poly(2-bromoaniline)-bromide salt was proved to be a novel, efficient, reusable, cheaper and eco-friendly polymer-based solid acid catalyst in the reaction between aromatic amines and N-vinyl lactam under solvent-free conditions to provide 2-methyl-4-anilino-1,2,3,4-tetrahydroquinolines. These 2,4-disubstituted tetrahydroquinolines were synthesized with trans selectivity.

ChemInform Abstract: Efficient Method for the Synthesis of α,α′‐Bis(arylmethylidene) Cycloalkanones Catalyzed by Bromodimethylsulfonium Bromide.

AbstractThe title compounds (III) are simply obtained by crossed aldol condensation between aromatic aldehydes and ketones (I).

ChemInform Abstract: Bromodimethylsulfonium Bromide: A Brominating Reagent for the Conversion of Anthracene into 9,10‐Dibromoanthracene.

Abstract Bromodimethylsulfonium bromide (BDMS) was used as an efficient brominating reagent for the synthesis of 9,10-dibromoanthracene in dichloromethane. The desired products were obtained in excellent yields.

ChemInform Abstract: Bromodimethylsulfonium Bromide (BDMS)‐Catalyzed Synthesis of 1,5‐Benzodiazepines Using a Multi‐Component Reaction Strategy.

AbstractThe facile one‐pot procedure allows the synthesis of 1,5‐benzodiazepines from o‐phenylenediamines, aldehydes, and β‐keto esters under mild reaction conditions.

Efficient Method for the Synthesis of α,α′-Bis(arylmethylidene) Cycloalkanones Catalyzed by Bromodimethylsulfonium Bromide

Bromodimethylsulfonium bromide (BDMS)–catalyzed crossed aldol condensation between aromatic aldehydes and ketones is reported to access α,α′-bis(arylmethylidene) cycloalkanones at room temperature in good yields within 3–10 min. The salient features of this method are the simplicity of the procedure, the ready accessibility of the catalyst, and greater yields in relatively short reaction times. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]