Universität zu Köln

Yatham, Veera Reddy ORCID: 0000-0002-3967-5342, Neudoerfl, Joerg-M., Schloerer, Nils E. and Berkessel, Albrecht ORCID: 0000-0003-0470-7428 (2015). Carbene catalyzed umpolung of alpha,beta-enals: a reactivity study of diamino dienols vs. azolium enolates, and the characterization of advanced reaction intermediates. Chem. Sci., 6 (7). S. 3706 - 3712. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 2041-6539

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Abstract

Since their discovery by Bode and Glorius in 2004, N-heterocyclic carbene catalyzed conjugate umpolung reactions of alpha,beta-enals have been postulated to involve the formation of diamino dienols (homoenolates) and/or azolium enolates (enolates), typically followed by addition to electrophiles, e.g. Michael-acceptors. In this article, we provide evidence, for the first time, for the postulated individual and specific reactivity patterns of diamino dienols (gamma-C-C-bond formation) vs. azolium enolates (beta-C-C-bond formation). Our study is based on the pre-formation of well defined diamino dienols and azolium enolates, and the in situ NMR monitoring of their reactivities towards enone electrophiles. Additionally, reaction intermediates were isolated and characterized, inter alia by X-ray crystallography.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Yatham, Veera Reddy UNSPECIFIED orcid.org/0000-0002-3967-5342 UNSPECIFIED Neudoerfl, Joerg-M. UNSPECIFIED UNSPECIFIED UNSPECIFIED Schloerer, Nils E. UNSPECIFIED UNSPECIFIED UNSPECIFIED Berkessel, Albrecht UNSPECIFIED orcid.org/0000-0003-0470-7428 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-418482
DOI:	10.1039/c5sc01027f
Journal or Publication Title:	Chem. Sci.
Volume:	6
Number:	7
Page Range:	S. 3706 - 3712
Date:	2015
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	2041-6539
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 N-HETEROCYCLIC-CARBENE; DIELS-ALDER REACTIONS; ALPHA,BETA-UNSATURATED ALDEHYDES; GAMMA-BUTYROLACTONES; DIRECT ANNULATIONS; STEREOSELECTIVE-SYNTHESIS; STAUDINGER REACTION; 4+2 CYCLOADDITION; THIAMINE ACTION; ENALS Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/41848