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dc.contributor.author Lim, Daniel en_US
dc.contributor.author Wengryniuk, Sarah E. en_US
dc.contributor.author Coltart, Dr Don en_US
dc.date.accessioned 2011-06-21T17:26:38Z
dc.date.available 2011-06-21T17:26:38Z
dc.date.issued 2010 en_US
dc.identifier.citation Krenske,Elizabeth H.;Houk,K. N.;Lim,Daniel;Wengryniuk,Sarah E.;Coltart,Don M.. 2010. Origins of Stereoselectivity in the alpha-Alkylation of Chiral Hydrazones. Journal of Organic Chemistry 75(24): 8578-8584. en_US
dc.identifier.issn 0022-3263 en_US
dc.identifier.uri http://hdl.handle.net/10161/4064
dc.description.abstract Density functional theory calculations and experiment reveal the origin of stereoselectivity in the deprotonation-alkylation of chiral N-amino cyclic carbamate (ACC) hydrazones. When the ACC is a rigid, camphor-derived carbamate, the two conformations of the azaenolate intermediate differ in energy due to conformational effects within the oxazolidinone ring and steric interactions between the ACC and the azaenolate. An electrophile adds selectively to the less-hindered pi-face of the azaenolate. Although it was earlier reported that use of ACC auxiliaries led to a-alkylated ketones with er values of 82:18 to 98:2, B3LYP calculations predict higher stereosclectivity. Direct measurement of the dr of an alkylated hydrazone prior to removal of the auxiliary confirms this prediction; the removal of the auxiliary under the reported conditions can compromise the overall stereoselectivity of the process. en_US
dc.language.iso en_US en_US
dc.publisher AMER CHEMICAL SOC en_US
dc.relation.isversionof doi:10.1021/jo1019877 en_US
dc.subject lithio azaallylic systems en_US
dc.subject asymmetric-synthesis en_US
dc.subject acyclic ketones en_US
dc.subject enantioselective alkylation en_US
dc.subject organolithium compounds en_US
dc.subject ab-initio en_US
dc.subject density en_US
dc.subject cyclohexanone en_US
dc.subject solvation en_US
dc.subject anions en_US
dc.subject chemistry, organic en_US
dc.title Origins of Stereoselectivity in the alpha-Alkylation of Chiral Hydrazones en_US
dc.title.alternative en_US
dc.description.version Version of Record en_US
duke.date.pubdate 2010-12-17 en_US
duke.description.endpage 8584 en_US
duke.description.issue 24 en_US
duke.description.startpage 8578 en_US
duke.description.volume 75 en_US
dc.relation.journal Journal of Organic Chemistry en_US

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