Studies toward the total synthesis of phorboxazole A
Studies toward the total synthesis of a highly potent cytotoxic marine natural product, phorboxazole A, were conducted and resulted in a route to an advanced intermediate, C4-C32, for this purpose. A key feature of our approach is the stereoselective synthesis of two cis-2,6-disubstituted tetrahydro...
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ndltd-ORGSU-oai-ir.library.oregonstate.edu-1957-308612012-07-11T03:22:16ZStudies toward the total synthesis of phorboxazole AKuntiyong, PunlopPhorboxazoles -- SynthesisStudies toward the total synthesis of a highly potent cytotoxic marine natural product, phorboxazole A, were conducted and resulted in a route to an advanced intermediate, C4-C32, for this purpose. A key feature of our approach is the stereoselective synthesis of two cis-2,6-disubstituted tetrahydropyrans present in the macrolide portion of phorboxazole A by palladium (II) mediated intramolecular alkoxy carbonylation. This provided the C20-C32 and C9-C19 tetrahydropyran subunits of phorboxazole A. An attempt at diastereoselective formation of the third C5-C9 trans-2,6-disubstituted tetrahydropyran by hydride reduction of a C9 hemiketal was complicated by reduction of the C7 exocyclic olefin. However, the C5-C9 tetrahydropyran was constructed by an intramolecular etherification sequence using a novel allylsilane as the source of C4-C8 of the macrolactone. The studies carried out in the course of this thesis have set in place a major segment of the phorboxazole A structure; they require only the addition of the C1-C3 unit and minor functional group modifications to complete the macrolide portion of the molecule.Graduation date: 2004White, James D.2012-07-10T17:52:55Z2012-07-10T17:52:55Z2004-01-062004-01-06Thesis/Dissertationhttp://hdl.handle.net/1957/30861en_US |
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en_US |
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Phorboxazoles -- Synthesis |
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Phorboxazoles -- Synthesis Kuntiyong, Punlop Studies toward the total synthesis of phorboxazole A |
description |
Studies toward the total synthesis of a highly potent cytotoxic marine
natural product, phorboxazole A, were conducted and resulted in a route to
an advanced intermediate, C4-C32, for this purpose. A key feature of our
approach is the stereoselective synthesis of two cis-2,6-disubstituted
tetrahydropyrans present in the macrolide portion of phorboxazole A by
palladium (II) mediated intramolecular alkoxy carbonylation. This provided
the C20-C32 and C9-C19 tetrahydropyran subunits of phorboxazole A. An
attempt at diastereoselective formation of the third C5-C9 trans-2,6-disubstituted tetrahydropyran by hydride reduction of a C9 hemiketal was
complicated by reduction of the C7 exocyclic olefin. However, the C5-C9
tetrahydropyran was constructed by an intramolecular etherification
sequence using a novel allylsilane as the source of C4-C8 of the
macrolactone. The studies carried out in the course of this thesis have set
in place a major segment of the phorboxazole A structure; they require only
the addition of the C1-C3 unit and minor functional group modifications to
complete the macrolide portion of the molecule. === Graduation date: 2004 |
author2 |
White, James D. |
author_facet |
White, James D. Kuntiyong, Punlop |
author |
Kuntiyong, Punlop |
author_sort |
Kuntiyong, Punlop |
title |
Studies toward the total synthesis of phorboxazole A |
title_short |
Studies toward the total synthesis of phorboxazole A |
title_full |
Studies toward the total synthesis of phorboxazole A |
title_fullStr |
Studies toward the total synthesis of phorboxazole A |
title_full_unstemmed |
Studies toward the total synthesis of phorboxazole A |
title_sort |
studies toward the total synthesis of phorboxazole a |
publishDate |
2012 |
url |
http://hdl.handle.net/1957/30861 |
work_keys_str_mv |
AT kuntiyongpunlop studiestowardthetotalsynthesisofphorboxazolea |
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1716392552573173760 |