Please use this identifier to cite or link to this item: http://hdl.handle.net/10995/27228
Title: Metal-free α-amination of secondary amines: Computational and experimental evidence for azaquinone methide and azomethine ylide intermediates
Authors: Dieckmann, A.
Richers, M. T.
Platonova, A. Y.
Zhang, C.
Seidel, D.
Houk, K. N.
Issue Date: 2013
Citation: Metal-free α-amination of secondary amines: Computational and experimental evidence for azaquinone methide and azomethine ylide intermediates / A. Dieckmann, M. T. Richers, A. Y. Platonova [et al.] // Journal of Organic Chemistry. — 2013. — Vol. 78. — № 8. — P. 4132-4144.
Abstract: We have performed a combined computational and experimental study to elucidate the mechanism of a metal-free α-amination of secondary amines. Calculations predicted azaquinone methides and azomethine ylides as the reactive intermediates and showed that iminium ions are unlikely to participate in these transformations. These results were confirmed by experimental deuterium-labeling studies and the successful trapping of the postulated azomethine ylide and azaquinone methide intermediates. In addition, computed barrier heights for the rate-limiting step correlate qualitatively with experimental findings. © 2013 American Chemical Society.
Keywords: AZOMETHINE YLIDES
BARRIER HEIGHTS
EXPERIMENTAL EVIDENCE
EXPERIMENTAL STUDIES
IMINIUM IONS
RATE-LIMITING STEPS
REACTIVE INTERMEDIATE
SECONDARY AMINES
CHEMISTRY
ORGANIC COMPOUNDS
AMINES
AMINE
AZAQUINONE METHIDE
AZOMETHINE YLIDE
DEUTERIUM
MORPHOLINE
PIPERIDINE
PYRROLIDINE DERIVATIVE
REAGENT
UNCLASSIFIED DRUG
AMINATION
ARTICLE
COMPUTATIONAL FLUID DYNAMICS
CYCLIZATION
CYCLOADDITION
AMINATION
AMINES
AZA COMPOUNDS
AZO COMPOUNDS
METALS
QUINONES
STEREOISOMERISM
THIOSEMICARBAZONES
URI: http://hdl.handle.net/10995/27228
SCOPUS ID: 84876532805
WOS ID: WOS:000319708300017
PURE ID: 917284
ISSN: 0022-3263
DOI: 10.1021/jo400483h
Appears in Collections:Научные публикации, проиндексированные в SCOPUS и WoS CC

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