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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Main Author: Kuntiyong, Punlop
Other Authors: White, James D.
Language:en_US
Published: 2012
Subjects:
Online Access:http://hdl.handle.net/1957/30861
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spelling 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
collection NDLTD
language en_US
sources NDLTD
topic Phorboxazoles -- Synthesis
spellingShingle 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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