Selective oxidation of sulfides to sulfoxides and sulfones at room temperature using H2O2 and a Mo(VI) salt as catalyst
TL;DR: In this article, selective oxidation of sulfides to sulfoxides and sulfones is achieved by H 2 O 2 using MoO 2 Cl 2 as the catalyst, and various substituted sulfides having functional groups such as methyl, methoxy, bromo, nitro, alkene, alkyne, alcohol, ester, aldehyde and an oxime are successfully and selectively oxidized without affecting the sensitive functionalities.
About: This article is published in Tetrahedron Letters.The article was published on 2006-07-03. It has received 135 citations till now. The article focuses on the topics: Alkyne & Aldehyde.
Citations
More filters
TL;DR: This review highlights the most recent outcomes on ILs in several important typical oxidation reactions, arranged in the series of oxidation of sulfides, oxidation of alcohols, epoxidation of alkenes, Baeyer-Villiger oxidation reaction, and oxidation of alkanes, or their combinations.
Abstract: Selective oxidation has an important role in environmental and green chemistry (e.g., oxidative desulfurization of fuels and oxidative removal of mercury) as well as chemicals and intermediates chemistry to obtain high-value-added special products (e.g., organic sulfoxides and sulfones, aldehydes, ketones, carboxylic acids, epoxides, esters, and lactones). Due to their unique physical properties such as the nonvolatility, thermal stability, nonexplosion, high polarity, and temperature-dependent miscibility with water, ionic liquids (ILs) have attracted considerable attention as reaction solvents and media for selective oxidations and are considered as green alternatives to volatile organic solvents. Moreover, for easy separation and recyclable utilization, IL catalysts have attracted unprecedented attention as “biphasic catalyst” or “immobilized catalyst” by immobilizing metal- or nonmetal-containing ILs onto mineral or polymer supports to combine the unique properties of ILs (chemical and thermal stabili...
348 citations
TL;DR: The selective oxidation of thiols to disulfides and sulfides to sulfoxides using graphite oxide (GO), a heterogeneous carbocatalyst obtained from low cost, commercial starting materials is described, finding it to proceed rapidly and in good yield.
Abstract: The selective oxidation of thiols to disulfides and sulfides to sulfoxides using graphite oxide (GO), a heterogeneous carbocatalyst obtained from low cost, commercial starting materials is described. The aforementioned oxidation reactions were found to proceed rapidly (as short as 10 min in some cases) and in good yield (51–100%) (19 examples). No over-oxidation of the substrates was observed, and GO's heterogeneous nature facilitated isolation and purification of the target products.
210 citations
TL;DR: Alkyl and aryl sulfides are oxidized to the corresponding sulfoxides or sulfones in excellent yields with aqueous hydrogen peroxide in the presence of silica sulfuric acid as an efficient solid acid catalyst as discussed by the authors.
132 citations
TL;DR: In this article, a one-pot procedure for the synthesis of regioselectively functionalized indoles has been developed from commercially available o-nitrobenzaldehydes and phosphoranes.
Abstract: Reductive cyclization of nitrobiphenyls and nitrostyrenes to carbazoles and indoles, respectively, is carried out by triphenylphosphine under mild conditions catalyzed by a dichlorodioxomolybdenum(VI) complex. A one-pot procedure for the synthesis of regioselectively functionalized indoles has been developed from commercially available o-nitrobenzaldehydes and phosphoranes.
122 citations
TL;DR: The appeal of ylide chemistry is diminished by the negative implications of these strategies on reagent usage, waste production, and functional group tolerance.
Abstract: Sulfur ylides are potent reactive units which are utilized in synthetic chemistry for a variety of powerful carbon–carbon and carbon–heteroatom bond-forming reactions. The classical preparation of ylides depend on the use of “sacrificial functionality”: a leaving group is displaced by a sulfide with subsequent regioselective deprotonation of the resulting sulfonium salt [Eq. (1)]; or a sulfide is treated with a metal carbene, which is formed by the decomposition of a diazo compound with loss of molecular nitrogen [Eq. (2)]. The synthetic efficiency of such processes is also adversely affected by the manipulations required to introduce the precursor moiety. Consequently, the appeal of ylide chemistry is diminished by the negative implications of these strategies on reagent usage, waste production, and functional group tolerance.
117 citations
References
More filters
TL;DR: A Cook's tour of the organosulfur chemistry of the genus Allium, as represented, inter alia, by garlic (Allium sativum L.) and onion(Allium cepa L.). as discussed by the authors reported on the biosynthesis of the S-alk(en)yl-L-cysteine S-oxides (aroma and flavor precursors) in intact plants and on how upon cutting or crushing the plants these precursor are cleaved by allinase enzymes, giving sulfenic acids.
Abstract: A Cook's tour is presented of the organosulfur chemistry of the genus Allium, as represented, inter alia, by garlic (Allium sativum L.) and onion (Allium cepa L.). We report on the biosynthesis of the S-alk(en)yl-L-cysteine S-oxides (aroma and flavor precursors) in intact plants and on how upon cutting or crushing the plants these precursors are cleaved by allinase enzymes, giving sulfenic acids—highly reactive organosulfur intermediates. In garlic, 2-propenesulfenic acid gives allicin, a thiosulfinate with antibiotic properties, while in onion 1-propenesulfenic acid rearranges to the sulfine (Z)-propanethial S-oxide, the lachrymatory factor (LF) of onion. Highlights of onion chemistry include the assignment of stereochemistry to the LF and determination of the mechanism of its dimerization; the isolation, characterization, and synthesis of thiosulfinates which most closely duplicate the taste and aroma of the freshly cut bulb, and additional unusual compounds such as zwiebelanes (dithiabicyclo[2.1.1]hexanes), a bis-sulfine (a 1,4-butanedithial S,S′-dioxide), antithrombotic and antiasthmatic cepaenes (α-sulfinyl disulfides), and vic-disulfoxides. Especially noteworthy in the chemistry of garlic are the discovery of ajoene, a potent antithrombotic agent from garlic, and the elucidation of the unique sequence of reactions that occur when diallyl disulfide, which is present in steam-distilled garlic oil, is heated. Reaction mechanisms under discussion include [3, 3]- and [2, 3]-sigma-tropic rearrangements involving sulfur (e.g. sulfoxide-accelerated thio- and dithio-Claisen rearrangements) and cycloadditions involving thiocarbonyl systems. In view of the culinary importance of alliaceous plants as well as the unique history of their use in folk medicine, this survey concludes with a discussion of the physiological activity of the components of these plants: cancer prevention, antimicrobial activity, insect and animal attractive/repulsive activity, olfactory–gustatory–lachrymatory properties, effect on lipid metabolism, platelet aggregation inhibitory activity and properties associated with ajoene. And naturally, comments about onion and garlic induced bad breath and heartburn may not be overlooked.
959 citations
931 citations
TL;DR: In this article, the authors reviewed the oxidation of sulfides to sulfoxides by hydrogen peroxide and provided 120 references, 14 tables and 16 schemes and 6 figures, with a total of 6 figures.
359 citations
274 citations
Book•
01 Jan 1993
TL;DR: In this article, the authors discuss the precursory synthesis of sulphonyl carbanions, including simple alkyl and dialkyl synsets, and the reaction with epoxides.
Abstract: Chapter and selected section headings: Introduction to Sulphone Chemistry. The Preparation of Sulphones. Simple Alkyl Aryl and Dialkyl Sulphones. Oxidation of sulphides. Vinyl Sulphones. Ionic and radical additions to alkenes, alkynes and allenes. Allylic, Allenic, Alkynyl and Aryl Sulphones. Palladium-catalysed synthesis of allylic sulphones. Functionalised Sulphones. Hydroxy and alkoxy sulphones. Sulphonyl Carbanions. Introduction to Sulphonyl Carbanions. The structure of sulphonyl carbanions. Reactions of Simple Sulphonyl Carbanions. Alkylations. Reaction with epoxides. Reactions of Additionally Stabilised Sulphonyl Carbanions. Ketosulphones and related systems. Sulphonyl Polyanions. Polyanions from simple sulphones. Additions to Unsaturated Sulphones. Heteroatom Nucleophiles. Nitrogen nucleophiles. Non-Stabilised Organometallics. Enolates, Related Anions and Miscellaneous Carbon Nucleophiles. Cyclopropanations. Radical Additions. Rearrangements of Sulphones. Ring Expansions and Fragmentations. Sulphinate to Sulphone Rearrangements. 1,3-Rearrangements of Allylic Sulphones. The Truce-Smiles Rearrangement. Miscellaneous Rearrangements. Cycloaddition Chemistry of Unsaturated Sulphones. [2+2] Cycloadditions. [3+2] Cycloadditions. [4+2] Cycloadditions. Carbon-Carbon Double-Bond Formation by Sulphone Elimination. The Julia Olefination Reaction. Alternative beta-Eliminations of Sulphones. The Ramberg-Backlund Reaction. Chemistry of Cyclic Sulphones. Three-Membered Ring Sulphones. Four-Membered Ring Sulphones. Five-Membered Ring Sulphones. Functionalised Normal-Sized Rings. Larger Ring Sulphones. Desulphonylation. Simple Alkyl Aryl and Dialkyl Sulphones. Allylic Sulphones. Vinyl Sulphones. Functionalised Sulphones. Sulphone Reduction. Index.
251 citations