C-C fragmentation is both powerful and elegant. Capable of stereospecifically introducing sp1-sp1, sp2-sp2, and sp2-sp-sp2 bond connectivity, it is the key transformation that allows all of the chemistry described herein. This dissertation begins with a comprehensive review of C-C fragmentation, which notably uncovers the lost origins of this transformation. Extensions of its utility in complex terpene synthesis are presented next. An integrated routing strategy was realized in the divergent enantioselective synthesis of the core ring systems of the xeniolide, xenibellol, and florlide natural products. A more general synthetic route was developed to gain direct access to the previously restricted, diverse, semi-validated structure space of the xenicane superfamily, and more than forty xenicane congeners were synthesized. These include xeniolides, blumiolides, florlides, bridgehead olefins and epoxides, keto-enol tautomeric mixtures, and the deshydroxymethyl xeniolide framework. Several other terpene motifs were also prepared, including functionalized cyclopentanones, CD ring systems of 18-methoxy-18-oxo-17-ketosteroids, and nine-membered ring-opening products. Seven of these novel compounds were found to selectively induce Bak- and Bax-dependent apoptosis in precancerous immortalized baby mouse kidney epithelial cells.
|Advisor:||Williams, Lawrence J.|
|School:||Rutgers The State University of New Jersey - New Brunswick|
|Department:||Graduate School - New Brunswick|
|School Location:||United States -- New Jersey|
|Source:||DAI-B 75/04(E), Dissertation Abstracts International|
|Keywords:||Anticancer, Biosynthesis, Carbon-carbon fragmentation, Diterpene, Synthetic methods, Terpene, Total synthesis, Transannular|
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