Brancatelli, Giovanna

GAETA, CARMINE

Geremia, Silvano

LATTANZI, Alessandra

MENINNO, SARA

NERI, Placido

Parrella, Alessandro

TALOTTA, CARMEN

English

Archivio della Ricerca - Università di Salerno

Calix 2011--ì 3th ìnternationaì Conîerence on Calixarenes - Giardini Naxos $taly) 5-9 July 2015Oxidation of Sulfides to Sulfoxides and Sulfones with Hydrogen PeroxideA. Lattanzi," S Meninno," A. Parrella," G Brancatelli,b S Geremia,b C. Gaeta," C. Talotta" andP Neri,"" Diparlimento di Chimica e Biologia, Università di Salerno, Via Giovanni Paolo ll 132, 84084Fisci ano( Salerno), ltalyh Centro di Eccellenza in Biocistallografia, Dipaftimento di Scienze Chimiche e Farmaceutiche, UniversitàdiTrieste, via L Giorgiei 1, 34127 Tieste, ltalyE-mail: *gaeta@unisa.itPolyoxometalates (POMs) are nano-sized, functional inorganic clusters with differentcompositionsand structures, which have been applied in catalysis, medicine, and materialsscience.l Thanks totheir rich redox chemistry, they demonstrated to be suitable catalysts foroxidations of alkenes,alcohols and sulfides.2 Given the insolubility of POMs in many organicsolvents, a typical approachto enhance the scarce mass transfer between POMs and organicsubstrates has been based onexchange of the counterion with classical cation surfactants (e.g.tetrabutyl ammonium).Consequently, surfactant encapsulated POM complexes proved to bemore soluble and effectivecatalysts in oxidative processes. We have designed andcharacterized a polyoxomolybdate-calixarene hybrid3 (tetra-ammonium-calix[4]arene'IMo8026]4-)1 with a view to study itsperformance in oxidation reactions (Figure 1).Figure 1. X-Ray structure of POM-calixarene hybrid 1.The au consists of one tetracationic calixareneand twohalf of tetraanionic POM, A different Mo coordination is observed for the two centrosymmetricPOMstructures: the left one with all octahedral Mo and the right one with two Mo in tetrahedral geometry.The development of efficient, selective and environmentally friendly procedures of oxidationofsulfides to sulfoxides and sulfones is a highly active research area,adue to the importanceofthese products as synthetic intermediates, in pharmaceutical and petroleumindustry.lnterestingly, we found that compound I served as one of the most efficient POM-basedcatalysts in the oxidation of sulfides either to sulfoxides or sulfones, when working at only0.05%mol loading, using 30% H2O2 solution as the oxidant in acetonitrilelSpecial issue on "polyoxometalates", Chem. Rev. 1998, 982Mizuno, N ; Kamata, K; Yamaguchi,K Top Catal.2O1O,53, 876-893.s For an example of polyoxotungstate-calixarene hybrid, see: lshii, Y ; Takenaka, Y.; Konishi, KAngew Chem lnt. Ed 2004,43,2702-2705aLatlanzi, A in Comprehensive Organic Synfhesis (2nd edition), (Eds Knochel, P., Molander, G. A ),Oxford,Elsevier, 2014, 7, 837 -879Calix 2015 - '1:AssembVesicle aCalixarenes ataggregate incomplexi$'ln this workcarboxylic actdiscrete and vMicroscopy tfaggregates ofvesicle of 1 ewater-solubilittThese resultstdrug delivery :Figure l.ArncFIHelttunen, K .zZhou,Y;Li,fP14

Oxidation of Sulfides to Sulfoxides and Sulfones with Hydrogen Peroxide

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Oxidation of Sulfides to Sulfoxides and Sulfones with Hydrogen Peroxide

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