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

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DOIResolve DOI: http://doi.org/10.1021/jo990544n
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TypeArticle
Journal titleJournal of Organic Chemistry
ISSN0022-3263
Volume64
Issue16
Pages59935999; # of pages: 7
Subjectfluorine; article; chemical reaction; cyclization; kinetics; structure analysis
AbstractUsing 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.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276652
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Record identifier80b1f661-deb5-4920-b98d-32ee3610351e
Record created2015-10-13
Record modified2016-05-09
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