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

dc.contributor.authorO'Reilly, Kate
dc.contributor.authorGupta, Manoj K.
dc.contributor.authorGandhi, Hirenkumar
dc.contributor.authorKumar, Vydyula P.
dc.contributor.authorEccles, Kevin S.
dc.contributor.authorLawrence, Simon E.
dc.contributor.authorO'Sullivan, Timothy P.
dc.date.accessioned2017-12-18T12:17:03Z
dc.date.available2017-12-18T12:17:03Z
dc.date.issued2016-09
dc.date.updated2017-12-15T13:53:04Z
dc.description.abstractA 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.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationO'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: 10.2174/1385272820666160513164417en
dc.identifier.doi10.2174/1385272820666160513164417
dc.identifier.endpage2638en
dc.identifier.issn1385-2728
dc.identifier.issued24en
dc.identifier.journaltitleCurrent Organic Chemistryen
dc.identifier.startpage2633en
dc.identifier.urihttps://hdl.handle.net/10468/5185
dc.identifier.volume20en
dc.language.isoenen
dc.publisherBentham Science Publishersen
dc.rights© 2016 Bentham Science Publishers. The published manuscript is available at EurekaSelect via http://www.eurekaselect.com/openurl/content.php?genre=article&doi= 10.2174/1385272820666160513164417en
dc.subjectOrganocatalysisen
dc.subjectCinchonaen
dc.subjectPeroxidationen
dc.subjectPeroxyacidsen
dc.subjectPeroxyestersen
dc.subjectPeroxyalcoholsen
dc.subjectCycloperoxidesen
dc.titleCinchona-catalysed, enantioselective synthesis of β-Peroxycarboxylic acids, β-peroxyesters and β-peroxyalcoholsen
dc.typeArticle (peer-reviewed)en
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