Universität zu Köln

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

Full text not available from this repository.

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:	Creators Email ORCID ORCID Put Code Richers, Matthew T. UNSPECIFIED UNSPECIFIED UNSPECIFIED Breugst, Martin UNSPECIFIED orcid.org/0000-0003-0950-8858 UNSPECIFIED Platonova, Alena Yu. UNSPECIFIED UNSPECIFIED UNSPECIFIED Ullrich, Anja UNSPECIFIED UNSPECIFIED UNSPECIFIED Dieckmann, Arne UNSPECIFIED UNSPECIFIED UNSPECIFIED Houk, K. N. UNSPECIFIED UNSPECIFIED UNSPECIFIED Seidel, Daniel UNSPECIFIED orcid.org/0000-0001-6725-111X UNSPECIFIED
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:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language 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 CYCLIZATION Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/44046