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

DOI	Resolve DOI: https://doi.org/10.1021/jo990544n
Author	Search for: Li, A.; Search for: Shtarev, A.B.; Search for: Smart, B.E.; Search for: Yang, Z.-Y.; Search for: Lusztyk, J.¹; Search for: Ingold, K. U.¹; Search for: Bravo, A.¹; Search for: Dolbier Jr., W.R.
Affiliation	National Research Council Canada
Format	Text, Article
Subject	fluorine; chemical reaction; cyclization; kinetics; structure analysis
Abstract	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.
Publication date	1999
In	Journal of Organic Chemistry 64, no. 16 (1999): 5993–5999.
Language	English
Peer reviewed	Yes
NPARC number	21276652
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Record identifier	80b1f661-deb5-4920-b98d-32ee3610351e
Record created	2015-10-13
Record modified	2020-03-20