Asymmetric peroxidation of α,β-unsaturated aldehydes under diarylprolinol ether catalysis

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dc.contributor.authorO'Reilly, Kate
dc.contributor.authorGupta, Manoj K.
dc.contributor.authorGandhi, Hirenkumar
dc.contributor.authorKumar, Vydyula P.
dc.contributor.authorO'Sullivan, Timothy P.
dc.contributor.funderIrish Research Councilen
dc.contributor.funderHorizon 2020en
dc.date.accessioned2018-12-03T14:52:55Z
dc.date.available2018-12-03T14:52:55Z
dc.date.issued2017
dc.date.updated2018-11-27T16:58:04Z
dc.description.abstractBackground: Chiral peroxides, many of which are biologically active, are an attractive target in organic synthesis. Organocatalysts have been used for some time in the asymmetric epoxidation of α,β- unsaturated carbonyls. More recently, cinchona-derived organocatalysts have been adapted to effect the asymmetric peroxidation of unsaturated ketones. We successfully applied this catalyst system to the stereoselective peroxidation of more challenging α,β-unsaturated aldehydes with moderate enantioselectivity observed. Herein we describe our efforts to improve upon the overall stereoselectivity using prolinol-derived organocatalysts. Objective: To determine whether diarylprolinol silyl ethers are effective catalysts in the asymmetric peroxidation of α,β-unsaturated aldehydes. Methods: Using trans-2-butenal as the test substrate, peroxidation with tert-butyl hydroperoxide was attempted in a range of different solvents. The resulting β-peroxyaldehydes were oxidised in situ to afford stable β-peroxyesters. The reaction was further optimised by varying the co-catalyst and by changing the silyl ether group on the prolinol catalyst. A number of short-chain substrates were subjected to peroxidation under optimised conditions. Results: Diarylprolinol ethers were found to be effective catalysts for the enantioselective peroxidation of unsaturated aldehydes. The degree of enantioselectivity was influenced both by the choice of solvent and acid cocatalyst. Furthermore, a clear trend emerged where the level of enantioselectivity increased with increasing steric bulk of the silyl group. Conclusion: Diarylprolinol ethers are effective catalysts for the asymmetric peroxidation of α,β-unsaturated aldehydes. Under optimised conditions, short-chain substrates may be converted to the corresponding β- peroxyesters in good yields and excellent enantioselectivities.en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationO’Reilly, K., Gupta, M. K., Gandhi, H., Kumar*, V. P. and O’Sullivan, T. P. (2017) 'Asymmetric peroxidation of α,β-unsaturated aldehydes under diarylprolinol ether catalysis', Current Organic Chemistry, 21(19), pp. 2013-2016. doi: 10.2174/1385272821666170412113323en
dc.identifier.doi10.2174/1385272821666170412113323
dc.identifier.endpage2016en
dc.identifier.issn1385-2728
dc.identifier.issn1875-5348
dc.identifier.issued19en
dc.identifier.journaltitleCurrent Organic Chemistryen
dc.identifier.startpage2013en
dc.identifier.urihttps://hdl.handle.net/10468/7167
dc.identifier.volume21en
dc.language.isoenen
dc.publisherBentham Science Publishersen
dc.relation.projectinfo:eu-repo/grantAgreement/EC/H2020::MSCA-IF-EF-ST/655508/EU/COMMANDEER: Disrupting microbial resistance using rationally designed signalling molecules/COMMANDEERen
dc.relation.projectinfo:eu-repo/grantAgreement/EC/FP7::SP3::PEOPLE/272194/EU/Towards an enantioselective synthesis of Plakortide P and its application to the development of drugs for the treatment of Chagas disease/PLAKORTIDEen
dc.relation.urihttp://www.eurekaselect.com/151532/article
dc.rights© 2017 Bentham Science. The published manuscript is available at EurekaSelect via http://www.eurekaselect.com/151532/articleen
dc.subjectOrganocatalysisen
dc.subjectProlinolen
dc.subjectAsymmetricen
dc.subjectPeroxidationen
dc.subjectPeroxyacidsen
dc.subjectPeroxyestersen
dc.titleAsymmetric peroxidation of α,β-unsaturated aldehydes under diarylprolinol ether catalysisen
dc.typeArticle (peer-reviewed)en
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