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Intramolecular carbozincation of unactivated alkenes occurs through a zinc radical transfer mechanism

Cohen, T and Gibney, H and Ivanov, R and Yeh, EAH and Marek, I and Curran, DP (2007) Intramolecular carbozincation of unactivated alkenes occurs through a zinc radical transfer mechanism. Journal of the American Chemical Society, 129 (49). 15405 - 15409. ISSN 0002-7863

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The cyclizations of a number of terminally unsaturated alkenyl zinc iodides to cyclopentylmethylzinc iodides, formerly believed to be nonradical in nature, have been revealed as radical chain cyclizations initiated by adventitious oxygen. Five cases are presented in which the published carbozincation cis/trans selectivities are essentially the same as those found for the cyclizations of the unsaturated alkyl iodide precursors of the alkylzinc iodides by the iodine atom transfer method at approximately the same temperatures. In addition, it has been found that one of the organozinc cyclizations does not occur in a system in which oxygen has been rigorously excluded. The combined findings strongly suggest that these organozinc cyclizations occur by a zinc radical transfer mechanism rather than by a conventional carbometallation that is thought to occur with the analogous organolithium and organomagnesium cyclizations. © 2007 American Chemical Society.


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Item Type: Article
Status: Published
CreatorsEmailPitt UsernameORCID
Cohen, Tcohen@pitt.eduCOHEN
Gibney, H
Ivanov, R
Yeh, EAH
Marek, I
Curran, DPcurran@pitt.eduCURRAN
Date: 12 December 2007
Date Type: Publication
Journal or Publication Title: Journal of the American Chemical Society
Volume: 129
Number: 49
Page Range: 15405 - 15409
DOI or Unique Handle: 10.1021/ja076554k
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0002-7863
PubMed ID: 17988132
Date Deposited: 08 Apr 2013 17:19
Last Modified: 05 Feb 2019 06:55


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