Guo, Binbin
(2013)
Catalytic Asymmetric Bond Constructions in Complex Molecule Synthesis. An Approach to the Synthesis of Spirolide C and the Development of Enantioselective Enolate Hydroxylation Reactions.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
The asymmetric synthesis of spirolide C, a highly potent marine toxin, has been investigated in our laboratory. The construction of C7-C28 bis-spiroketal was completed through a strategy utilizing an intermolecular Stetter reaction and a biomimetic ketalization process. Stereocenters were set in great diastereo- and enantioselectivity via asymmetric catalysis. The efficiency of the synthesis was demonstrated by its convergency and high yields.
A cinchona alkaloid catalyzed ketene-oxaziridine cyclocondensation has been developed to provide an access to enantioenriched α-hydroxy carbonyl compounds. The oxazolidinones arising from the cyclocondensation were converted to various α-hydroxy carbonyl compounds via nucleophilic ring openings. Greater than 98% ee was achieved in oxazolidinone formation and the subsequent ring openings proceeded with retention of the ee or minor epimerization.
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Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
|
| Date: |
25 January 2013 |
| Date Type: |
Publication |
| Defense Date: |
3 December 2012 |
| Approval Date: |
25 January 2013 |
| Submission Date: |
29 November 2012 |
| Access Restriction: |
No restriction; Release the ETD for access worldwide immediately. |
| Number of Pages: |
129 |
| 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: |
spirolides, natural product synthesis, asymmetric catalysis, enolate hydroxylation, cinchona alkaloid catalysts, oxaziridines, oxazolidinones, acid chlorides, cyclocondensation |
| Date Deposited: |
25 Jan 2013 19:41 |
| Last Modified: |
15 Nov 2016 14:07 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/16511 |
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