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

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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 O'Sullivan, Timothy P.
dc.date.accessioned 2018-12-03T14:52:55Z
dc.date.available 2018-12-03T14:52:55Z
dc.date.issued 2017
dc.identifier.citation O’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: 10.2174/1385272821666170412113323 en
dc.identifier.volume 21 en
dc.identifier.issued 19 en
dc.identifier.startpage 2013 en
dc.identifier.endpage 2016 en
dc.identifier.issn 1385-2728
dc.identifier.issn 1875-5348
dc.identifier.uri http://hdl.handle.net/10468/7167
dc.identifier.doi 10.2174/1385272821666170412113323
dc.description.abstract Background: 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.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher Bentham Science Publishers en
dc.relation.uri http://www.eurekaselect.com/151532/article
dc.rights © 2017 Bentham Science. The published manuscript is available at EurekaSelect via http://www.eurekaselect.com/151532/article en
dc.subject Organocatalysis en
dc.subject Prolinol en
dc.subject Asymmetric en
dc.subject Peroxidation en
dc.subject Peroxyacids en
dc.subject Peroxyesters en
dc.title Asymmetric peroxidation of α,β-unsaturated aldehydes under diarylprolinol ether catalysis en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother Timothy P. 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 2018-11-27T16:58:04Z
dc.description.version Accepted Version en
dc.internal.rssid 415487123
dc.contributor.funder Irish Research Council en
dc.contributor.funder Horizon 2020 en
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.relation.project info:eu-repo/grantAgreement/EC/H2020::MSCA-IF-EF-ST/655508/EU/COMMANDEER: Disrupting microbial resistance using rationally designed signalling molecules/COMMANDEER en
dc.relation.project info: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/PLAKORTIDE en


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