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dc.contributor.authorMyers, Eddie L.
dc.contributor.authorPalte, Michael J.
dc.contributor.authorRaines, Ronald T
dc.date.accessioned2020-01-24T16:32:49Z
dc.date.available2020-01-24T16:32:49Z
dc.date.issued2019-01
dc.date.submitted2018-10
dc.identifier.issn0022-3263
dc.identifier.issn1520-6904
dc.identifier.urihttps://hdl.handle.net/1721.1/123680
dc.description.abstractThe identification and understanding of structure–activity relationships is vital for rational catalyst design. A kinetic study of the hydrogen–deuterium exchange reaction of cyclohexanone in aqueous solution, as catalyzed by proline derivatives, has revealed valuable structure–activity relationships. In phosphate-buffered solution, cis-4-fluoroproline is more active than the trans isomer, a distinction that appears to originate from a destabilizing interaction between the fluorine atom and phosphate anion during general acid-catalyzed dehydration of the carbinolamine intermediate. trans-4-Ammoniumprolines are exceptionally active catalysts owing to favorable Coulombic interactions involving the ammonium group and the alkoxide moiety formed upon 1,2-addition of the proline derivative to the ketone. These results could be used for the optimization of proline catalysts, especially in transformations where the formation of the putative iminium ion is rate-limiting.en_US
dc.description.sponsorshipNational Institutes of Health (U.S.). (Grant R01 AR044276)en_US
dc.description.sponsorshipNational Institutes of Health (U.S.). (Grant R01 GM04478)en_US
dc.language.isoen
dc.publisherAmerican Chemical Society (ACS)en_US
dc.relation.isversionofhttp://dx.doi.org/10.1021/acs.joc.8b02644en_US
dc.rightsArticle is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.en_US
dc.sourcePMCen_US
dc.titleCatalysis of Hydrogen–Deuterium Exchange Reactions by 4-Substituted Proline Derivativesen_US
dc.typeArticleen_US
dc.identifier.citationMyers, Eddie L. et al. "Catalysis of Hydrogen–Deuterium Exchange Reactions by 4-Substituted Proline Derivatives." Journal of Organic Chemistry 84, 3 (January 2019): 1247-1256 © 2019 American Chemical Societyen_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemistryen_US
dc.relation.journalJournal of Organic Chemistryen_US
dc.eprint.versionAuthor's final manuscripten_US
dc.type.urihttp://purl.org/eprint/type/JournalArticleen_US
eprint.statushttp://purl.org/eprint/status/PeerRevieweden_US
dc.date.updated2020-01-07T15:10:58Z
dspace.date.submission2020-01-07T15:11:00Z
mit.journal.volume84en_US
mit.journal.issue3en_US


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