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A Stereochemical Comparison Between Radical Atom Transfer Cyclizations and Organozinc Cyclizations of Primary and Secondary Hexenyl Iodides

Gibney, Heather Marie (2006) A Stereochemical Comparison Between Radical Atom Transfer Cyclizations and Organozinc Cyclizations of Primary and Secondary Hexenyl Iodides. Master's Thesis, University of Pittsburgh. (Unpublished)

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Cyclized hexenylzinc iodides have been reported to give different cis:trans product ratios than the analogous radical cyclized hexenyl iodides and this has been taken as evidence that the organozinc and not radical cyclizations are involved. Unfortunately, temperature dependence was not taken into account when comparing the two sets of ratios. To further investigate these differing cis:trans ratios, three hexenyl iodides were synthesized and cyclized under radical atom transfer conditions between 5 °C and 80 °C. The resulting cis:trans product ratios were measured by gas chromatography. The cis:trans ratios observed ranged from high (i.e. cis:trans 1:13.3) to low (cis:trans 2.0:1); the selectivities decreased as the temperature increased. Comparison of cis:trans ratios of the products from the zinc cyclization to the cis:trans ratios of the products from the radical cyclizations at the same temperatures showed that the two sets of ratios were within experimental error of each other. It was concluded that the zinc mediated cyclizations of primary and secondary alkenyl iodides to give cyclopentylmethylzinc halides involve radical cyclizations.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Gibney, Heather Mariehmg7@pitt.eduHMG7
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairCurran, Dennis Pcurran@pitt.eduCURRAN
Committee MemberFloreancig, Paulflorean@pitt.eduFLOREAN
Committee MemberCohen, Theodorecohen@pitt.eduCOHEN
Date: 28 September 2006
Date Type: Completion
Defense Date: 24 July 2006
Approval Date: 28 September 2006
Submission Date: 4 August 2006
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: MS - Master of Science
Thesis Type: Master's Thesis
Refereed: Yes
Uncontrolled Keywords: atom transfer; hexenyl iodide; organozinc; radical
Other ID:, etd-08042006-085451
Date Deposited: 10 Nov 2011 19:56
Last Modified: 15 Nov 2016 13:48


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