Total synthesis of Galbulimima alkaloids. Resin-bound glycosyl phosphates as glycosyl donors.
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2006.
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| Format: | Thesis |
| Language: | eng |
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Massachusetts Institute of Technology
2007
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| Online Access: | http://hdl.handle.net/1721.1/38321 |
| _version_ | 1826210881976926208 |
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| author | Hunt, Diana Katharine |
| author2 | Mohammad Movassaghi and Peter H. Seeberger. |
| author_facet | Mohammad Movassaghi and Peter H. Seeberger. Hunt, Diana Katharine |
| author_sort | Hunt, Diana Katharine |
| collection | MIT |
| description | Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2006. |
| first_indexed | 2024-09-23T14:56:57Z |
| format | Thesis |
| id | mit-1721.1/38321 |
| institution | Massachusetts Institute of Technology |
| language | eng |
| last_indexed | 2024-09-23T14:56:57Z |
| publishDate | 2007 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/383212019-04-12T14:05:30Z Total synthesis of Galbulimima alkaloids. Resin-bound glycosyl phosphates as glycosyl donors. Hunt, Diana Katharine Mohammad Movassaghi and Peter H. Seeberger. Massachusetts Institute of Technology. Dept. of Chemistry. Massachusetts Institute of Technology. Dept. of Chemistry. Chemistry. Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2006. Vita. Includes bibliographical references. I. Total Synthesis of Galbulimima Alkaloids. The total synthesis of enantiomerically enriched (+)- and (-)-galbulimima alkaloid 13 is outlined. Sequential use of catalytic cross-coupling and cross-metathesis reactions followed by an intramolecular Diels-Alder reaction provided the required trans-decalin AB ring system and masked the C16-carbonyl as an N-vinyl carbamate for late stage oxidative unveiling as the corresponding C16-enone. Completely diastereoselective introduction of the C-ring via radical cyclization chemistry followed by an enamine-ketone addition for construction of the CDE-ring system allowed rapid entry to the pentacyclic core of these alkaloids. The absolute stereochemistry of natural (-)-galbulimima alkaloid 13 is now unambiguously revised to 2S. (cont.) II. Resin-bound Glycosyl Phosphates As Glycosyl Donors. Resin-bound glycosyl phosphates were readily accessed on solid support via a three step procedure from support-bound glycals. These resin-bound glycosyl phosphates were successfully used as glycosylating agents for coupling with a series of solution based nucleophiles. The stereochemical outcome of disaccharide formation was dependent on the nature of the linker connecting the saccharide to the polymer. Interestingly, other glycosyl donors such as thioglycosides and trichloroacetimidates did not exhibit this dependence, indicating a different reaction mechanism for glycosylation. III. A Modular Synthesis of FGF-2 Binding Heparin Pentasaccharide. A modular synthesis of FGF-2 binding heparin pentasaccharide is outlined. The synthetic strategy utilizes a disaccharide trichloroacetimidate donor and a uronic acid acceptor as building blocks designed for later application to a fully automated synthesis. by Diana Katharine Hunt. Ph.D. 2007-08-03T18:29:49Z 2007-08-03T18:29:49Z 2006 2006 Thesis http://hdl.handle.net/1721.1/38321 154317092 eng M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582 413 p. application/pdf Massachusetts Institute of Technology |
| spellingShingle | Chemistry. Hunt, Diana Katharine Total synthesis of Galbulimima alkaloids. Resin-bound glycosyl phosphates as glycosyl donors. |
| title | Total synthesis of Galbulimima alkaloids. Resin-bound glycosyl phosphates as glycosyl donors. |
| title_full | Total synthesis of Galbulimima alkaloids. Resin-bound glycosyl phosphates as glycosyl donors. |
| title_fullStr | Total synthesis of Galbulimima alkaloids. Resin-bound glycosyl phosphates as glycosyl donors. |
| title_full_unstemmed | Total synthesis of Galbulimima alkaloids. Resin-bound glycosyl phosphates as glycosyl donors. |
| title_short | Total synthesis of Galbulimima alkaloids. Resin-bound glycosyl phosphates as glycosyl donors. |
| title_sort | total synthesis of galbulimima alkaloids resin bound glycosyl phosphates as glycosyl donors |
| topic | Chemistry. |
| url | http://hdl.handle.net/1721.1/38321 |
| work_keys_str_mv | AT huntdianakatharine totalsynthesisofgalbulimimaalkaloidsresinboundglycosylphosphatesasglycosyldonors |