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231224s2011 xx |||||o 00| ||eng c |
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|a 10.1002/jcc.21768
|2 doi
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|a pubmed24n0690.xml
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|a (DE-627)NLM20712485X
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|a (NLM)21455961
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|a DE-627
|b ger
|c DE-627
|e rakwb
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|a eng
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| 100 |
1 |
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|a Kim, Jongtaek
|e verfasserin
|4 aut
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|a Electronic and chelation effects on the unusual C2-methylation of N-(para-substituted)phenylaziridines with lithium organocuprates
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|c 2011
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|a Text
|b txt
|2 rdacontent
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|a ƒaComputermedien
|b c
|2 rdamedia
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|a ƒa Online-Ressource
|b cr
|2 rdacarrier
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|a Date Completed 24.08.2011
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|a Date Revised 21.11.2013
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|a published: Print-Electronic
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|a Citation Status MEDLINE
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|a Copyright © 2011 Wiley Periodicals, Inc.
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|a 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∼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∼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 3δ- 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
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|a Journal Article
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|a Research Support, Non-U.S. Gov't
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|a Aziridines
|2 NLM
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|a Chelating Agents
|2 NLM
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|a Organometallic Compounds
|2 NLM
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|a Lithium
|2 NLM
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|a 9FN79X2M3F
|2 NLM
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| 700 |
1 |
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|a Yoo, Eunjung
|e verfasserin
|4 aut
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1 |
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|a Chang, Sukbok
|e verfasserin
|4 aut
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| 700 |
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|a Lee, Yoon Sup
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 32(2011), 9 vom: 15. Juli, Seite 1859-68
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
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|g volume:32
|g year:2011
|g number:9
|g day:15
|g month:07
|g pages:1859-68
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|u http://dx.doi.org/10.1002/jcc.21768
|3 Volltext
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