Sulfur Oxidation Increases the Rate of HIRE-Type [1.4]Thiazepinone Ring Expansion and Influences the Conformation of a Medium-Sized Heterocyclic Scaffold.

Autor:	Reutskaya E; Institute of Chemistry, Saint Petersburg State University, Saint Petersburg 199034, Russia., Sapegin A; Institute of Chemistry, Saint Petersburg State University, Saint Petersburg 199034, Russia., Peintner S; Department of Chemistry - BMC, Uppsala University, SE-751 23 Uppsala, Sweden., Erdélyi M; Department of Chemistry - BMC, Uppsala University, SE-751 23 Uppsala, Sweden., Krasavin M; Institute of Chemistry, Saint Petersburg State University, Saint Petersburg 199034, Russia.
Jazyk:	angličtina
Zdroj:	The Journal of organic chemistry [J Org Chem] 2021 Apr 16; Vol. 86 (8), pp. 5778-5791. Date of Electronic Publication: 2021 Apr 07.
DOI:	10.1021/acs.joc.1c00236
Abstrakt:	The hydrated imidazoline ring expansion (HIRE-type) reaction was investigated for a series of di(hetero)arene-fused [1.4]thiazepinones in comparison with their sulfone counterparts. The sulfones were found to undergo ring expansion at a much higher rate compared to the thioethers, much in line with the current mechanistic understanding of the process. Moreover, the amide bond cis - and trans -isomers of the ring-expanded products were found, in the case of sulfones, to be stabilized through an intramolecular hydrogen bond. The latter phenomenon was studied in detail by NMR experiments and corroborated by X-ray crystallographic information.
Databáze:	MEDLINE
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