Cyclizations of 5-hexenyl, 6-heptenyl, 7-octenyl, and 8-nonenyl radicals. The kinetic and regiochemical impact of fluorine and oxygen substituents

Par Conseil national de recherches du Canada

DOI	Trouver le DOI : https://doi.org/10.1021/jo990544n
Auteur	Rechercher : Li, A.; Rechercher : Shtarev, A.B.; Rechercher : Smart, B.E.; Rechercher : Yang, Z.-Y.; Rechercher : Lusztyk, J.¹; Rechercher : Ingold, K. U.¹; Rechercher : Bravo, A.¹; Rechercher : Dolbier Jr., W.R.
Affiliation	Conseil national de recherches du Canada
Format	Texte, Article
Sujet	fluorine; chemical reaction; cyclization; kinetics; structure analysis
Résumé	Using competition kinetic methodology, rate constants for cyclizations of a series of hydrofluorocarbon (HFC) and ether 5-hexenyl, 6-heptenyl, and 7-octenyl radicals have been determined. Remarkably large rate constants (> 107 s-1) have been observed for 6-exo-cyclizations of 1,1,2,2-tetrafluoro- and 1,1,2,2,3,3,4,4,-octafluoro-6-heptenyl radicals (> 103 those of analogous hydrocarbon radicals), whereas HFC hexenyl and heptenyl ethers exhibit lower cyclization reactivity, as do HFC 7-octenyl radical systems, which cyclize in an endo manner. HFC 8-nonenyl radicals were not observed to cyclize. The results can be rationalized in terms of transition state polar influences, though other factors may also play significant roles.
Date de publication	1999
Dans	Journal of Organic Chemistry 64, nº 16 (1999) : 5993–5999.
Langue	anglais
Publications évaluées par des pairs	Oui
Numéro NPARC	21276652
Exporter la notice	Exporter en format RIS
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Identificateur de l’enregistrement	80b1f661-deb5-4920-b98d-32ee3610351e
Enregistrement créé	2015-10-13
Enregistrement modifié	2020-03-20

Date de modification :: 2024-04-18