Painter, Thomas Oliver
(2009)
Cycloisomerization and Carbocyclization Reactions of Allenes for the Synthesis of Cross-Conjugated Trienes and Tryptophan-Derived Scaffolds.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
A strategy for the preparation of 3-vinyl-2-alkylidene-3-cyclohexen-1-ones has been developed using an intramolecular rhodium(I)-catalyzed carbocyclization reaction of allene-ynones. Application of this strategy towards the preparation of analogs of the anticancer agent irofulven was realized, leading to highly functionalized spiro[2.5]octatrienes.A novel approach to ε-lactams from allene-containing propargyl amides has been achieved, also using the rhodium(I)-catalyzed carbocyclization reaction. Further elaboration of this strategy has afforded triene-containing azepines and a pyrroloazepinone.A diverging diversity-oriented synthesis (DOS) strategy using tryptophan as a key starting material was investigated. Constructon of allenic tetrahydro-β-carboline scaffolds via a Pictet-Spengler reaction and subsequent silver(I)-catalyzed cycloisomerization afforded tetrahydroindolizinoindoles. Conversion of the tetrahydro-β-carboline to an allenic propiolamide followed by a microwave-assisted allenic [2 + 2] cycloaddition reaction provided tetrahydrocyclobutaindoloquinolizinones. An allene-yne substituted derivative of tryptophan gave indolylmethylazabicyclooctadiene when subjected to a microwave-assisted allenic [2 + 2] cycloaddition reaction. This same tryptophan-derived precursor afforded an indolylmethyldihydrocyclopentapyridinone when subjected to a rhodium(I)-catalyzed cyclocarbonylation reaction.
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Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
| Creators | Email | Pitt Username | ORCID  |
|---|
| Painter, Thomas Oliver | topst3@pitt.edu | TOPST3 | |
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| ETD Committee: |
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| Date: |
17 June 2009 |
| Date Type: |
Completion |
| Defense Date: |
18 March 2009 |
| Approval Date: |
17 June 2009 |
| Submission Date: |
11 March 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-yne; carbocyclization; cycloaddition; cyclocarbonylation; cycloisomerization; lactams; transition metal |
| Other ID: |
http://etd.library.pitt.edu/ETD/available/etd-03112009-122213/, etd-03112009-122213 |
| Date Deposited: |
10 Nov 2011 19:32 |
| Last Modified: |
15 Nov 2016 13:37 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/6482 |
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