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Title: Efforts Toward the Synthesis of Maoecrystal V and Atropurpuran with the Discovery of Novel Skeletal Rearrangements
Authors: Smith, Michael
Advisors: Sorensen, Erik J
Contributors: Chemistry Department
Subjects: Chemistry
Organic chemistry
Issue Date: 2013
Publisher: Princeton, NJ : Princeton University
Abstract: Synthetic strategies and efforts towards two complex diterpene natural products, maoecrystal V and atropurpuran are described. Novel skeletal rearrangements that were observed during the travails of the latter are reported. The first chapter describes efforts to synthesize the bioactive diterpenoid, maoecrystal V in enantiopure fashion starting from (+)-limonene oxide. An intramolecular Rh(II)-catalyzed C-H insertion reaction installed the tetrahydrofuran ring with requisite stereochemistry. The chemistry culminated with the installation of all desired atoms albeit with unsuccessful attempts to install the desired δ-lactone. The last chapter presents efforts to make the fused double bicyclo[2.2.2]octane containing diterpene, atropurpuran. Initial attempts to forge the skeletal core of the system were proposed to use cascading [4+2] cycloaddition chemistry. After it became apparent that the first strategy would unlikely be successful, a slightly reworked strategy provided the first synthetically made fused double bicyclo[2.2.2]octane molecule in low yield. Then a major strategy shift to attempt to make desired ring system via cascading radicals generated from arylsulfonyl hydrazones, led to an unexpected skeletal rearrangement under neutral conditions. A few examples of this novel reaction are presented. A second unexpected reaction forming a tricyclic-azo-compound occurred when attempting to expand the scope of the first C-C insertion reaction.
Alternate format: The Mudd Manuscript Library retains one bound copy of each dissertation. Search for these copies in the library's main catalog
Type of Material: Academic dissertations (Ph.D.)
Language: en
Appears in Collections:Chemistry

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