Effect of Ring Strain on the Thiolate−Disulfide Exchange. A Computational Study

Autor:	Debbie C. Mulhearn, Steven M. Bachrach, Joshua T Woody
Rok vydání:	2002
Předmět:	Ring size Addition reaction Reaction mechanism Nucleophile Chemistry Stereochemistry Organic Chemistry SN2 reaction Ring (chemistry) Cleavage (embryo) Ring strain
Zdroj:	The Journal of Organic Chemistry. 67:8983-8990
ISSN:	1520-6904 0022-3263
DOI:	10.1021/jo026223k
Popis:	B3LYP/aug-cc-pVDZ and MP2/6-31+G calculations of the reactions of HS(-) with small cyclic disulfides (dithiirane, 1,2-dithietane, 1,2-dithiolane, and 1,2-dithiane) were performed to determine the reaction mechanism. For the five- and six-membered rings, the reaction proceeds via the addition-elimination pathway, consistent with acyclic analogues. The smaller, more strained three- and four-membered rings react by the S(N)2 mechanism. Addition of the nucleophile cannot be accommodated by the small rings without concomitant ring cleavage.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::02c12709493f98d9afe49b8db43c7c6f https://doi.org/10.1021/jo026223k Zobrazit plný text záznamu