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(Unpublished)
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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Item Type: |
University of Pittsburgh ETD
|
Status: |
Unpublished |
Creators/Authors: |
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ETD Committee: |
Title | Member | Email Address | Pitt Username | ORCID |
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Committee Chair | Brummond, Kay | | | | Committee Member | Day, Billy | | | | Committee Member | Curran, Dennis | | | | Committee Member | Floreancig, Paul | | | |
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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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