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The Allenic Carbocyclization Reaction of Allene-ynes: Progress towards the Syntheses of Fumagillol and Ovalicin

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DeForrest, Jolie E (2009) The Allenic Carbocyclization Reaction of Allene-ynes: Progress towards the Syntheses of Fumagillol and Ovalicin. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Abstract

The Rh(I)-catalyzed allenic carbocyclization reaction is a powerful strategy for the assembly of densely functionalized cyclic cross-conjugated trienes. This methodology exhibits excellent functional group compatibility, and allows for the construction of five-, six-, and seven-membered rings in high yields from allene-yne precursors. In this thesis, progress towards the total synthesis of (-)-fumagillol and (-)-ovalicin is reported. The entire carbocyclic skeleton of both structurally related natural products has been synthesized in a single synthetic transformation via an allenic carbocyclization reaction. It is anticipated that the allylic hydroxyl group of the functionalized cross-conjugated can be used for the chemo- and stereoselective installation of epoxides and hydroxyl groups incorporated in both sesquiterpenes.The constitutional group selectivity of the â-hydride elimination step in the allenic carbocyclization reaction has been investigated. We found that TMS-alkynyl allenes with an appending isobutylene group can be reacted under Rh(I)-catalyzed allenic carbocyclization reaction conditions to afford regioisomerically pure cross-conjugated trienes in good yields. The examples within, indicate that a coordinating alkene can be incorporated into the allene-yne substrate to control the â-hydride elimination step of the cyclization reaction to yield trienes with a 1,1-disubstituted alkene side chain.


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Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
DeForrest, Jolie Ejed20@pitt.eduJED20
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairBrummond, Kay
Committee MemberDay, Billy
Committee MemberCurran, Dennis
Committee MemberFloreancig, Paul
Date: 9 June 2009
Date Type: Completion
Defense Date: 14 April 2009
Approval Date: 9 June 2009
Submission Date: 13 April 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: allene-ynes; fumagillol; ovalicin
Other ID: http://etd.library.pitt.edu/ETD/available/etd-04132009-212646/, etd-04132009-212646
Date Deposited: 10 Nov 2011 19:37
Last Modified: 15 Nov 2016 13:40
URI: http://d-scholarship.pitt.edu/id/eprint/7128

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