Plakortide E (85), which is isolated from the Jamaican marine sponge Plakortis halichondrioides, contains a five-membered peroxide ring, with the oxygen atoms are linked to tertiary C4 and C6 centers.34,57 In this thesis, the total synthesis of plakortide E (85) is described. A novel palladium-catalyzed approach towards 1,2-dioxolanes has been developed. A lipase-catalyzed kinetic resolution was employed to provide optically pure 1,2-dioxolane central cores. Coupling of the central cores and side chains was achieved by a Negishi reaction. All four isomeric structures of plakortide E methyl ester, namely, 86a-d were synthesized, and one of these molecules, 86d proved to be natural plakortide E methyl ester on the basis of 1H, 13C NMR spectra and specific rotation. With plakortide E methyl ester (4S,6R, 10R)-(-)- cis-(86d) and its other three isomers in hand, we successfully converted them into plakortone B (3S,4S,6 R,10R)-(87a), and its isomers ent-87a, 87b and ent-87b via an intramolecular oxa-Michael addition/lactonization cascade reaction. Saponification converted 1,2-dioxolane 86d into plakortide E (85a) whose absolute configuration (4S,6 R,10R) was confirmed by comparison of spectral and physical data with those previously reported.35b / Sun, Xiaoyu. / Adviser: Henry N. C. Wong. / Source: Dissertation Abstracts International, Volume: 73-06, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references (leaves 183-195). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_344842 |
| Date | January 2011 |
| Contributors | Sun, Xiaoyu, Chinese University of Hong Kong Graduate School. Division of Chemistry. |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, theses |
| Format | electronic resource, microform, microfiche, 1 online resource (xi, 290 leaves : ill.) |
| Rights | Use of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/) |
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