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dc.contributor.advisorParker, Kathlyn , Drueckhammer, Daleen_US
dc.contributor.authorCalder, Matthewen_US
dc.contributor.otherDepartment of Chemistryen_US
dc.date.accessioned2013-05-22T17:34:15Z
dc.date.available2013-05-22T17:34:15Z
dc.date.issued1-Aug-12en_US
dc.date.submitted12-Augen_US
dc.identifierCalder_grad.sunysb_0771E_11113en_US
dc.identifier.urihttp://hdl.handle.net/1951/59594
dc.description287 pg.en_US
dc.description.abstractNovel Ways to Generate Polypropionates for the Synthesis of Polyketide Natural Products by Matthew Edward Calder Doctor of Philosophy in Chemistry Stony Brook University 2012 Polyketide natural products are desirable targets due to their interesting biological and pharmacological properties. Polyketides contain synthetically challenging propionate subunits, which are comprised of alternating methyl and hydroxyl stereogenic centers. The synthesis of polypropionate subunits is the central theme of this work. The first project focused on employing the stereopentad and stereotetrad of the broad-spectrum antibiotic oleandomycin for the total synthesis of the polyketide natural product discodermolide. Our strategy involved a deconstruction/reconstruction process to access the polypropionate fragments that could then be modified to known discodermolide intermediates. Unfortunately, the unavailability of oleandomycin made completing this project difficult. The second project focused on developing a new methodology employing cyclic hydroboration for the stereoselective synthesis of stereopentad fragments. Cyclic hydroboration has been a little used technique in organic synthesis. However, it has been shown to be an effective method for generating simple acyclic compounds that contain remote stereogenic centers in a single step. To date, the cyclic hydroboration of 1,5-dienes has not been employed to synthesize stereopentad subunits. Utilizing work done on model systems in our group and literature precedents, we designed and synthesized a series of structurally complex acyclic dienes. Cyclic hydroboration of the complex dienes afforded stereopentads in moderate to high yields and diastereoselectivity. The reaction installs three of the five contiguous stereocenters in a single step. This work demonstrates that cyclic hydroboration can be an effective way to generate stereopentads. The synthesis, optimization and potential application of this methodology for the synthesis of polyketide natural products are discussed.en_US
dc.description.sponsorshipStony Brook University Libraries. SBU Graduate School in Department of Chemistry. Charles Taber (Dean of Graduate School).en_US
dc.formatElectronic Resourceen_US
dc.language.isoen_USen_US
dc.publisherThe Graduate School, Stony Brook University: Stony Brook, NY.en_US
dc.subject.lcshChemistryen_US
dc.titleNovel Ways to Generate Polypropionates for the Synthesis of Polyketide Natural Productsen_US
dc.typeDissertationen_US
dc.description.advisorAdvisor(s): Parker, Kathlyn ; Drueckhammer, Dale. Committee Member(s): Ojima, Iwao ; Lau, Roland.en_US
dc.mimetypeApplication/PDFen_US


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