Please use this identifier to cite or link to this item: http://hdl.handle.net/10995/75539
Title: Redox-neutral α-oxygenation of amines: Reaction development and elucidation of the mechanism
Authors: Richers, M. T.
Breugst, M.
Platonova, A. Y.
Ullrich, A.
Dieckmann, A.
Houk, K. N.
Seidel, D.
Issue Date: 2014
Publisher: American Chemical Society
Citation: Redox-neutral α-oxygenation of amines: Reaction development and elucidation of the mechanism / M. T. Richers, M. Breugst, A. Y. Platonova et al. // Journal of the American Chemical Society. — 2014. — Vol. 136. — Iss. 16. — P. 6123-6135.
Abstract: Cyclic secondary amines and 2-hydroxybenzaldehydes or related ketones react to furnish benzo[e][1,3]oxazine structures in generally good yields. This overall redox-neutral amine α-C-H functionalization features a combined reductive N-alkylation/oxidative α-functionalization and is catalyzed by acetic acid. In contrast to previous reports, no external oxidants or metal catalysts are required. Reactions performed under modified conditions lead to an apparent reductive amination and the formation of o-hydroxybenzylamines in a process that involves the oxidation of a second equivalent of amine. A detailed computational study employing density functional theory compares different mechanistic pathways and is used to explain the observed experimental findings. Furthermore, these results also reveal the origin of the catalytic efficiency of acetic acid in these transformations. © 2014 American Chemical Society.
Keywords: ACETIC ACID
KETONES
PH
2-HYDROXYBENZALDEHYDES
C-H FUNCTIONALIZATION
CATALYTIC EFFICIENCIES
COMPUTATIONAL STUDIES
FUNCTIONALIZATIONS
MECHANISTIC PATHWAYS
MODIFIED CONDITIONS
REDUCTIVE AMINATION
AMINES
ACETAL DERIVATIVE
ACETIC ACID
AMINE
AMPHOLYTE
BENZYLAMINE
CARBONYL DERIVATIVE
ISOQUINOLINE DERIVATIVE
KETONE
METAL
OXIDIZING AGENT
SALICYLALDEHYDE
TOLUENE
AMINE
OXYGEN
ALKYLATION
AMINATION
ARTICLE
CATALYSIS
CATALYST
CYCLOADDITION
DENSITY FUNCTIONAL THEORY
ENERGY
HYDROGEN BOND
ISOMERIZATION
OXIDATION REDUCTION REACTION
OXYGENATION
PROTON NUCLEAR MAGNETIC RESONANCE
REACTION ANALYSIS
REACTION OPTIMIZATION
REDUCTION
TEMPERATURE DEPENDENCE
CHEMICAL STRUCTURE
CHEMISTRY
CONFORMATION
OXIDATION REDUCTION REACTION
AMINES
CATALYSIS
KETONES
MODELS, MOLECULAR
MOLECULAR CONFORMATION
OXIDATION-REDUCTION
OXYGEN
TOLUENE
URI: http://hdl.handle.net/10995/75539
metadata.dc.rights: info:eu-repo/semantics/openAccess
SCOPUS ID: 84899538013
WOS ID: WOS:000335086100049
PURE ID: 374355
ISSN: 0002-7863
DOI: 10.1021/ja501988b
Appears in Collections:Научные публикации, проиндексированные в SCOPUS и WoS CC

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