Redox-neutral α-oxygenation of amines: reaction development and elucidation of the mechanism
| Autor: | Martin Breugst, Matthew T. Richers, Alena Yu. Platonova, Anja Ullrich, Daniel Seidel, Arne Dieckmann, Kendall N. Houk |
|---|---|
| Rok vydání: | 2014 |
| Předmět: |
Models
Molecular PH Molecular Conformation OXIDIZING AGENT 2-HYDROXYBENZALDEHYDES 01 natural sciences Biochemistry Oxygen Reductive amination C-H FUNCTIONALIZATION ENERGY chemistry.chemical_compound REACTION OPTIMIZATION Colloid and Surface Chemistry KETONE CHEMISTRY Models Organic chemistry CATALYTIC EFFICIENCIES AMPHOLYTE DENSITY FUNCTIONAL THEORY Amines MODELS MOLECULAR ISOMERIZATION CATALYST SALICYLALDEHYDE BENZYLAMINE Ketones CONFORMATION AMINATION ACETAL DERIVATIVE METAL OXIDATION REDUCTION REACTION Amine gas treating Density functional theory Oxidation-Reduction CYCLOADDITION MECHANISTIC PATHWAYS TEMPERATURE DEPENDENCE REDUCTIVE AMINATION chemistry.chemical_element FUNCTIONALIZATIONS ALKYLATION 010402 general chemistry Redox AMINE Article Catalysis Acetic acid CARBONYL DERIVATIVE ACETIC ACID MODIFIED CONDITIONS ARTICLE REACTION ANALYSIS 010405 organic chemistry OXYGENATION CHEMICAL STRUCTURE HYDROGEN BOND COMPUTATIONAL STUDIES Molecular General Chemistry Toluene Combinatorial chemistry 0104 chemical sciences PROTON NUCLEAR MAGNETIC RESONANCE REDUCTION chemistry ISOQUINOLINE DERIVATIVE Chemical Sciences |
| Zdroj: | Journal of the American Chemical Society, vol 136, iss 16 Journal of the American Chemical Society |
| Popis: | 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. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|