Cinchona-catalysed, enantioselective synthesis of β-Peroxycarboxylic acids, β-peroxyesters and β-peroxyalcohols

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dc.contributor.author O'Reilly, Kate
dc.contributor.author Gupta, Manoj K.
dc.contributor.author Gandhi, Hirenkumar
dc.contributor.author Kumar, Vydyula P.
dc.contributor.author Eccles, Kevin S.
dc.contributor.author Lawrence, Simon E.
dc.contributor.author O'Sullivan, Timothy P.
dc.date.accessioned 2017-12-18T12:17:03Z
dc.date.available 2017-12-18T12:17:03Z
dc.date.issued 2016-09
dc.identifier.citation O'Reilly, K., Gupta, M. K., Gandhi, H, Eccles, K. S., Lawrence, S. E. and O'Sullivan T. P. (2016) 'Cinchona-catalysed, Enantioselective Synthesis of β-Peroxycarboxylic Acids, β-Peroxyesters and β-Peroxyalcohols', Current Organic Chemistry, 20(24), pp. 2633-2638. doi: 10.2174/1385272820666160513164417 en
dc.identifier.volume 20 en
dc.identifier.issued 24 en
dc.identifier.startpage 2633 en
dc.identifier.endpage 2638 en
dc.identifier.issn 1385-2728
dc.identifier.uri http://hdl.handle.net/10468/5185
dc.identifier.doi 10.2174/1385272820666160513164417
dc.description.abstract A cinchona-catalysed, enantioselective oxa-Michael reaction of α,β-unsaturated aldehydes with either tert-butyl hydroperoxide or cumene hydroperoxide was developed. The reaction was optimised by screening of solvents, modification of the catalyst framework and variation of the acid co-catalysts. A strong relationship was noted between the pKa of the acid co-catalyst and the degree of selectivity. Enantioselective peroxidation of α,β- unsaturated aldehydes with tert-butyl hydroperoxide afforded β-peroxyaldehydes with good enantioselectivities. In situ oxidation of the latter compounds furnished β-peroxycarboxylic acids in high yields. Enantiomeric excesses were determined by derivitisation to their mandelate esters and subsequent separation by chiral high performance liquid chromatography. Peroxidation with cumene hydroperoxide was similarly successful with the products being isolated as stable β-peroxyalcohols. These latter β-peroxyalcohols offer a direct route to 5-membered, chiral cycloperoxides via a silver-mediated cyclisation. This reaction proceeds by trapping of the oxygen lone pair by the incipient carbocation followed by loss of the cumyl or tert-butyl group and formation of the cycloperoxide product. en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher Bentham Science Publishers en
dc.rights © 2016 Bentham Science Publishers. The published manuscript is available at EurekaSelect via http://www.eurekaselect.com/openurl/content.php?genre=article&doi= 10.2174/1385272820666160513164417 en
dc.subject Organocatalysis en
dc.subject Cinchona en
dc.subject Peroxidation en
dc.subject Peroxyacids en
dc.subject Peroxyesters en
dc.subject Peroxyalcohols en
dc.subject Cycloperoxides en
dc.title Cinchona-catalysed, enantioselective synthesis of β-Peroxycarboxylic acids, β-peroxyesters and β-peroxyalcohols en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother Tim O'Sullivan, School Of Pharmacy, University College Cork, Cork, Ireland. +353-21-490-3000 Email: tim.osullivan@ucc.ie en
dc.internal.availability Full text available en
dc.date.updated 2017-12-15T13:53:04Z
dc.description.version Accepted Version en
dc.internal.rssid 363936089
dc.description.status Peer reviewed en
dc.identifier.journaltitle Current Organic Chemistry en
dc.internal.copyrightchecked Yes en
dc.internal.licenseacceptance Yes en
dc.internal.IRISemailaddress tim.osullivan@ucc.ie en
dc.internal.IRISemailaddress simon.lawrence@ucc.ie en


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