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Radical Cations in Synthesis: Utilizing an Electron Transfer-Initiated Cyclization Toward the Natural Product Apicularen A

Poniatowski, Alexander James (2009) Radical Cations in Synthesis: Utilizing an Electron Transfer-Initiated Cyclization Toward the Natural Product Apicularen A. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Abstract

Reported herein is a synthetic campaign toward the vacuolar ATPase inhibitor apicularen A through an oxidative cyclization protocol. In this protocol (termed Electron Transfer-Initiated Cyclization, or ETIC), highly reactive oxocarbenium ions are generated through benzylic carbon-carbon σ-bond cleavage under chemically mild conditions. Regioselective cleavage of one homobenzylic ether in the presence of another homobenzylic ether is achieved by selectively weakening one carbon-carbon σ-bond through substitution. This work demonstrates that if bond cleavage is sufficiently rapid following oxidation, then oxidative fragmentation reactions can be used to generate stable cations selectively in the presence of other readily oxidized functional groups

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Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Poniatowski, Alexander Jamesajp24@pitt.eduAJP24
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairFloreancig, Paul Eflorean@pitt.eduFLOREAN
Committee MemberWilcox, Craig Sdaylite@pitt.eduDAYLITE
Committee MemberHildebrand, Jeffrey Djeffh@pitt.eduJEFFH
Committee MemberBrummond, Kay Mkbrummon@pitt.eduKBRUMMON
Date: 30 September 2009
Date Type: Completion
Defense Date: 14 July 2009
Approval Date: 30 September 2009
Submission Date: 12 August 2009
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: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: cytotoxin; macrolactone; macrolide lactone; tetrahydropyrone
Other ID: http://etd.library.pitt.edu/ETD/available/etd-08122009-170020/, etd-08122009-170020
Date Deposited: 10 Nov 2011 19:59
Last Modified: 15 Nov 2016 13:48
URI: http://d-scholarship.pitt.edu/id/eprint/9067

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