Richers, Matthew T., Breugst, Martin ORCID: 0000-0003-0950-8858, Platonova, Alena Yu., Ullrich, Anja, Dieckmann, Arne, Houk, K. N. and Seidel, Daniel ORCID: 0000-0001-6725-111X (2014). Redox-Neutral alpha-Oxygenation of Amines: Reaction Development and Elucidation of the Mechanism. J. Am. Chem. Soc., 136 (16). S. 6123 - 6136. WASHINGTON: AMER CHEMICAL SOC. ISSN 1520-5126

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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 alpha-C--H functionalization features a combined reductive N-alkylation/oxidative alpha-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.

Item Type: Journal Article
Creators:
CreatorsEmailORCIDORCID Put Code
Richers, Matthew T.UNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Breugst, MartinUNSPECIFIEDorcid.org/0000-0003-0950-8858UNSPECIFIED
Platonova, Alena Yu.UNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Ullrich, AnjaUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Dieckmann, ArneUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Houk, K. N.UNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Seidel, DanielUNSPECIFIEDorcid.org/0000-0001-6725-111XUNSPECIFIED
URN: urn:nbn:de:hbz:38-440466
DOI: 10.1021/ja501988b
Journal or Publication Title: J. Am. Chem. Soc.
Volume: 136
Number: 16
Page Range: S. 6123 - 6136
Date: 2014
Publisher: AMER CHEMICAL SOC
Place of Publication: WASHINGTON
ISSN: 1520-5126
Language: English
Faculty: Unspecified
Divisions: Unspecified
Subjects: no entry
Uncontrolled Keywords:
KeywordsLanguage
DOPAMINE D-3/D-2 RECEPTORS; FISCHER CARBENE COMPLEXES; H BOND FUNCTIONALIZATION; NONRACEMIC BETTI BASE; IMINIUM ION ROUTE; ONE-POT SYNTHESIS; AZOMETHINE YLIDES; ASYMMETRIC-SYNTHESIS; SECONDARY-AMINES; INTRAMOLECULAR CYCLIZATIONMultiple languages
Chemistry, MultidisciplinaryMultiple languages
URI: http://kups.ub.uni-koeln.de/id/eprint/44046

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