You, Lingfeng
(2006)
SYNTHETIC EFFORTS TOWARDS INGENOL CROSS-CONJUGATED TRIENES AND THEIR APPLICATION TO RAPID INCREASES IN MOLECULAR COMPLEXITY.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
Synthesis of the ingenol skeleton using a Pauson-Khand reaction as the key step was investigated. Although the Pauson-Khand reaction failed to provide the highly strained ingenol skeleton, several relatively complex Pauson-Khand precursors were prepared in about ten steps. The scope and limitation of the Pauson-Khand reaction in accessing highly strained molecules were studied. A rhodium(I)-catalyzed allenic Alder-ene reaction was developed that provides cross-conjugated trienes in good yields. This method shows enticing functional group compatibility, and progress has been made to increase the stereoselectivity of the olefinic side chain via iridium(I) catalysis. A consecutive one-pot Alder-ene/[4+2]/[4+2] reaction has been developed to demonstrate the potential of the cross-conjugated triene for accessing polycyclic compounds. The reaction sequence is highly selective with the Alder-ene and the first Diels-Alder reaction only providing a single isomer and the intermolecular [4+2] cycloaddition giving two endo addition products resulting from addition of the dienophile to either face of the diene. The transformation is highly atom-efficient with all the atoms of the starting dialkynyl allenes and the dienophiles appearing in the products.
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Details
| Item Type: |
University of Pittsburgh ETD
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| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
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| Date: |
30 March 2006 |
| Date Type: |
Completion |
| Defense Date: |
2 August 2005 |
| Approval Date: |
30 March 2006 |
| Submission Date: |
1 September 2005 |
| 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: |
Alder-ene; cross-conjugated triene; ingenol; rhodium |
| Other ID: |
http://etd.library.pitt.edu/ETD/available/etd-09012005-105944/, etd-09012005-105944 |
| Date Deposited: |
10 Nov 2011 20:01 |
| Last Modified: |
15 Nov 2016 13:50 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/9310 |
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