Universität zu Köln

Paul, Mathias ORCID: 0000-0003-4635-3605, Neudoerfl, Joerg-M. and Berkessel, Albrecht ORCID: 0000-0003-0470-7428 (2019). Breslow Intermediates from a Thiazolin-2-ylidene and Fluorinated Aldehydes: XRD and Solution-Phase NMR Spectroscopic Characterization. Angew. Chem.-Int. Edit., 58 (31). S. 10596 - 10601. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1521-3773

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Abstract

The first generation and X-ray diffraction (XRD) analysis of a crystalline Breslow intermediate (BI) derived from a thiazolin-2-ylidene, that is, the aromatic heterocycle present in vitamin B-1, is reported. Key to success was the combined use of pentafluorobenzaldehyde and a thiazolin-2-ylidene carrying an enol-stabilizing dispersion energy donor as N-substituent. A so-called primary intermediate (PI) could be isolated in protonated form (pPI) as well and analyzed by XRD. Furthermore, the first stable BI derived from an aromatic thiazolin-2-ylidene and an aliphatic aldehyde (trifluoroacetaldehyde) was prepared and characterized by NMR spectroscopy in solution. When switching to a saturated thiazolidin-2-ylidene, reaction with pentafluorobenzaldehyde afforded a new BI in solution (NMR spectroscopy). Attempts to crystallize the latter BI resulted in the isolation of a novel thiazolidin-2-ylidene dimer that had undergone rearrangement to a hexahydro[1,4]-thiazino[3,2-b]-1,4-thiazine.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Paul, Mathias UNSPECIFIED orcid.org/0000-0003-4635-3605 UNSPECIFIED Neudoerfl, Joerg-M. UNSPECIFIED UNSPECIFIED UNSPECIFIED Berkessel, Albrecht UNSPECIFIED orcid.org/0000-0003-0470-7428 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-134546
DOI:	10.1002/anie.201904308
Journal or Publication Title:	Angew. Chem.-Int. Edit.
Volume:	58
Number:	31
Page Range:	S. 10596 - 10601
Date:	2019
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	1521-3773
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 CARBENE-CATALYZED UMPOLUNG; CRYSTAL-STRUCTURE; THIAMINE ACTION; MECHANISM; STEREOCHEMISTRY; REACTIVITY; DISPERSION; CHEMISTRY Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/13454