DC Field | Value | Language |
---|---|---|
dc.contributor.author | Kim, Jong-Taek | ko |
dc.contributor.author | Yoo, Eun-Jung | ko |
dc.contributor.author | Chang, Suk-Bok | ko |
dc.contributor.author | Lee, Yoon-Sup | ko |
dc.date.accessioned | 2013-03-11T04:22:15Z | - |
dc.date.available | 2013-03-11T04:22:15Z | - |
dc.date.created | 2012-02-06 | - |
dc.date.created | 2012-02-06 | - |
dc.date.created | 2012-02-06 | - |
dc.date.issued | 2011-07 | - |
dc.identifier.citation | JOURNAL OF COMPUTATIONAL CHEMISTRY, v.32, no.9, pp.1859 - 1868 | - |
dc.identifier.issn | 0192-8651 | - |
dc.identifier.uri | http://hdl.handle.net/10203/98239 | - |
dc.description.abstract | Density functional theory calculations with the B3LYP functional were performed for the title ring-opening reaction to understand the intrinsic activating and directing effects of the N-substituents, as well as the electron donating effect of the para-substituted (Y = Cl, H, Me) phenyl group at the more hindered benzylic C2 atom. The N-tosyl group (i.e., N-Tos) or the N-(2-pyridyl)sulfonyl group (i.e., N-Py) was introduced to activate the ring nitrogen atom (N1) and the para-substituted (Y = Cl, H, Me) phenyl group for the activation of the C2 atom. Conformational searches and geometry optimizations were performed for the N-(para-substituted)phenylaziridines (1 similar to 6). Calculations indicate that the aziridine 6 (i.e., Py/Me) has the most elongated C2-N1 bond intrinsically due to the electronic activating effects, implying the aziridine 6 to be the most potent candidate for the more-hindered C2 opening. Transition states (TSs) were investigated for the prospective ring-opening paths (I similar to IV), considering the types of intermolecular push-pull interactions between the N-activated phenylaziridines and the cuprate. The N-Py group provides an unique C2-favored TS along the path IV, which the N-Tos group cannot afford, due to the less charge transfer from the nucleophilic CH(3)(delta-) of the cuprate into the electrophilic C2 atom. Furthermore, the e-donating effect of the para-substituents (Y = Cl, H, Me) enhances the C2 opening for the path IV. This study enables us to understand the unusual ring-opening phenomena in terms of electronic and directing effects and hence may serve as a tool to design substrates for highly regioselective ring openings. (C) 2011 Wiley Periodicals, Inc. J Comput Chem 32: 1859-1868, 2011 | - |
dc.language | English | - |
dc.publisher | WILEY-BLACKWELL | - |
dc.subject | RING-OPENING REACTIONS | - |
dc.subject | NUCLEOPHILIC-SUBSTITUTION REACTIONS | - |
dc.subject | CYSTEINE PROTEASE INHIBITORS | - |
dc.subject | SOLUBLE EPOXIDE HYDROLASE | - |
dc.subject | BETA-ALKOXY ALCOHOLS | - |
dc.subject | REACTION-MECHANISM | - |
dc.subject | AMINO-ACIDS | - |
dc.subject | 3-MEMBERED HETEROCYCLES | - |
dc.subject | THEORETICAL APPROACH | - |
dc.subject | CARBON NUCLEOPHILES | - |
dc.title | Electronic and Chelation Effects on the Unusual C2-Methylation of N-(para-Substituted)Phenylaziridines with Lithium Organocuprates | - |
dc.type | Article | - |
dc.identifier.wosid | 000290531000008 | - |
dc.identifier.scopusid | 2-s2.0-84962424367 | - |
dc.type.rims | ART | - |
dc.citation.volume | 32 | - |
dc.citation.issue | 9 | - |
dc.citation.beginningpage | 1859 | - |
dc.citation.endingpage | 1868 | - |
dc.citation.publicationname | JOURNAL OF COMPUTATIONAL CHEMISTRY | - |
dc.embargo.liftdate | 9999-12-31 | - |
dc.embargo.terms | 9999-12-31 | - |
dc.contributor.localauthor | Chang, Suk-Bok | - |
dc.contributor.localauthor | Lee, Yoon-Sup | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordAuthor | ring-opening reactions | - |
dc.subject.keywordAuthor | DFT calculations | - |
dc.subject.keywordAuthor | aziridine ring opening | - |
dc.subject.keywordAuthor | reaction mechanism | - |
dc.subject.keywordAuthor | cuprate catalyst | - |
dc.subject.keywordPlus | RING-OPENING REACTIONS | - |
dc.subject.keywordPlus | NUCLEOPHILIC-SUBSTITUTION REACTIONS | - |
dc.subject.keywordPlus | CYSTEINE PROTEASE INHIBITORS | - |
dc.subject.keywordPlus | SOLUBLE EPOXIDE HYDROLASE | - |
dc.subject.keywordPlus | BETA-ALKOXY ALCOHOLS | - |
dc.subject.keywordPlus | REACTION-MECHANISM | - |
dc.subject.keywordPlus | AMINO-ACIDS | - |
dc.subject.keywordPlus | 3-MEMBERED HETEROCYCLES | - |
dc.subject.keywordPlus | THEORETICAL APPROACH | - |
dc.subject.keywordPlus | CARBON NUCLEOPHILES | - |
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