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14529493
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190819s2018 xx |||||om||||||| ||eng d
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9780438973343
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(MiAaPQ)AAI13850202
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AAI13850202
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14529493
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MiAaPQ
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eng
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Schuppe, Alexander William.
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Total Syntheses of Andirolide N, Xylogranatopyridine B, and Granatumine A.
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[electronic resource].
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Ann Arbor :
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ProQuest Dissertations & Theses,
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2018.
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1 online resource (439 p.)
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Source: Dissertations Abstracts International, Volume: 80-09, Section: B.
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Publisher info.: Dissertation/Thesis.
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Thesis (Ph.D.)--Yale University, 2018.
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Access restricted by licensing agreement.
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This item is not available from ProQuest Dissertations & Theses.
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Chapter one of this thesis discusses the biosynthesis, isolation, structural diversity and therapeutic potential of the limonoid natural products. This chapter also details the state-of-the-art in the total syntheses of limonoids, which primarily relies on linear polyolefin cyclizations. As a point of departure, a fragment based coupling approach is discussed as a strategy to quickly assembly the limonoid scaffold. Chapter two details the first application of a fragment coupling approach toward the synthesis of the limonoid natural products. Andirolide N and a related limonoid congener, 8a-hydroxycarapin were quickly accessed through the strategic use of a degraded limonoid, iso-odoratin. Employing iso-odoratin allowed for late-stage installation of the challenging A-ring architecture present in andirolide N. The final step of this route demonstrates the chemical feasibility of our biosynthetic proposal that andirolide N arises from 8α-hydroxycarapin. The completion of these syntheses necessitated the development of several methodologies, such as ozonolytic β-fragmentation, the use of Gold's reagents for the preparation of enaminones and a copper-catalyzed aerobic γ-hydroxylation of carbonyl compounds. The third chapter pertains to the total synthesis of the limonoid alkaloids, which are proposed to arise biosynthetically from a mexicanolide-type limonoids, such as 8ahydroxycarapin. The total synthesis of xylogranatopyridine B relied on a convergent stannyl-Liebeskind pyridine synthesis to forge the central pyridine ring. The stannane fragment was prepared by a novel allyl-palladium catalyzed oxidative β-stannylation of enones. Additionally, the synthesis of the challenging bislactone lirnonoid alkaloids relied on a unique pyran to pyridine interconversion.
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Access is available to the Yale community.
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Chemistry.
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Yale University.
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http://id.loc.gov/authorities/names/n79043367
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Dissertations & Theses @ Yale University.
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Dissertations Abstracts International
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80-09B.
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Online resource
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Online thesis
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https://yale.idm.oclc.org/login?URL=http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqm&rft_dat=xri:pqdiss:13850202
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Yale Internet Resource
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Yale Internet Resource >> None|DELIM|14527854
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online resource
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2019-08-21T12:07:36.000Z
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DO NOT EDIT. DO NOT EXPORT.
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0
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http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqm&rft_dat=xri:pqdiss:13850202