Universität zu Köln

Goederz, Anna Schlundt nee, Hemmersbach, Lars, Romanski, Steffen, Neudoerfl, Joerg-Martin and Schmalz, Hans-Guenther ORCID: 0000-0003-0489-1827 (2022). Vinylogous Winstein Rearrangement: Unexpected Isomerization of an Azide-Substituted Cyclohexadiene-Fe(CO)3 Complex. Organometallics, 41 (21). S. 2997 - 3004. WASHINGTON: AMER CHEMICAL SOC. ISSN 1520-6041

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Abstract

In the course of our research into enzyme-triggered CO-releasing molecules (ET-CORMs), we were interested in using 2-acetoxy-5-azido-1,3-cyclohexadiene-Fe(CO)3 (rac-2) as a building block for further structural modification by means of Cu -catalyzed azide-alkyne cycloaddition (CuAAC click chemistry). Treatment of [2-acetoxy-cyclohexadienyl-Fe(CO)3]+[PF6]- with Zn(N3)2, TMS-N3, or NaN3 surprisingly afforded 2-acetoxy-1-azido-2,4-cyclohexadiene-Fe(CO)3 (rac-9) as the main product. We could show that rac-2 is primarily formed under kinetic control but undergoes a rapid isomerization to rac-9 (as the thermodynamic product) in a formal vinylogous Winstein rearrangement under concomitant migration of the Fe(CO)3 moiety. This unprecedented reaction displays a 1st order kinetics and appears to proceed via an ionic (rather than a concerted intramolecular) mechanism as supported by crossover experiments using deuterated compounds. The CuAAC reaction of rac-9 with propargylic alcohol afforded triazole rac-13, which was demonstrated (by headspace-gas chromatography (GC)) to act as an ET-CORM in the presence of porcine liver esterase.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Goederz, Anna Schlundt nee UNSPECIFIED UNSPECIFIED UNSPECIFIED Hemmersbach, Lars UNSPECIFIED UNSPECIFIED UNSPECIFIED Romanski, Steffen UNSPECIFIED UNSPECIFIED UNSPECIFIED Neudoerfl, Joerg-Martin UNSPECIFIED UNSPECIFIED UNSPECIFIED Schmalz, Hans-Guenther UNSPECIFIED orcid.org/0000-0003-0489-1827 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-659440
DOI:	10.1021/acs.organomet.2c00418
Journal or Publication Title:	Organometallics
Volume:	41
Number:	21
Page Range:	S. 2997 - 3004
Date:	2022
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1520-6041
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language 1ST TOTAL-SYNTHESIS; IRON TRICARBONYL COMPLEXES; CARBON-MONOXIDE; ORGANIC-SYNTHESIS; MOLECULES; CATIONS; ORGANOIRON; BIOLOGY; ROUTE Multiple languages Chemistry, Inorganic & Nuclear; Chemistry, Organic Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/65944