Exploring a Symmetry Based Logic for Palau'amine Synthesis
| dc.contributor.advisor | Harran, Patrick | en |
| dc.creator | Li, Qingyi | en |
| dc.date.accessioned | 2010-07-12T17:25:37Z | en |
| dc.date.accessioned | 2014-02-19T22:01:20Z | |
| dc.date.available | 2010-07-12T17:25:37Z | en |
| dc.date.available | 2014-02-19T22:01:20Z | |
| dc.date.issued | 2008-05-13 | en |
| dc.description.abstract | Palau'amine is a natural product originally isolated in 1993 from the marine sponge Stylotella aurantium. It is reported to posess impressive biological activities, including: antifungal, antibacterial, and antineoplastic characters. Moreover, it is a strong immunosuppressant (IC50<18ng/mL, allogenic lymphocyte reaction). The molecule has a complex polycyclic structure having a contiguous array of eight stereogenic centers. It is unusually rich in heteroatoms. A recent revision of its relating stereochemistry has brought further attention to this fascinating molecule. The current strategy of our group features a chlorination initiated cascade process on a symmetric precursor that assembles the skeleton of palau'amine with in a single operation. A symmetric bisalkylidene precursor for this process was synthesized. During the process, two new methodologies were developed: a titanocene dichloride mediated regioselective and stereoselective dimerization of heterocyclic dineolates; and a chemoselective Rh(I) carbene complexes catalyzed conjugation hydrosilylation of enamides. Our core idea was subsequently validated by the formation of the spirocyclopentane motif in palau'amine by an electrophilic halogen induced desymmetrization. | en |
| dc.format.digitalOrigin | born digital | en |
| dc.format.medium | Electronic | en |
| dc.format.mimetype | application/pdf | en |
| dc.identifier.other | en | |
| dc.identifier.uri | http://hdl.handle.net/2152.5/282 | en |
| dc.language.iso | en | en |
| dc.subject | Spiro Compounds | en |
| dc.subject | Guanidines | en |
| dc.subject | Alkaloids | en |
| dc.title | Exploring a Symmetry Based Logic for Palau'amine Synthesis | en |
| dc.type.genre | dissertation | en |
| dc.type.material | Text | en |
| thesis.date.available | 2009-05-13 | en |
| thesis.degree.department | en | |
| thesis.degree.discipline | Biological Chemistry | en |
| thesis.degree.grantor | Graduate School of Biomedical Sciences | en |
| thesis.degree.level | Ph.D. | en |
| thesis.degree.name | Doctor of Philosophy | en |