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Denmark, Scott E. Liu, Jack Hung-Chang 2015-09-25T22:14:03Z 2015-09-25T22:14:03Z 10000-01-01 2009 2009 A sequential rhodium-catalyzed silylcarbocyclization of enynes parlayed with a palladium-catalyzed, silicon-based cross-coupling reaction has been developed. 1,6-Enynes reacted with benzyldimethylsilane in the presence of rhodium catalysts to afford five-membered rings bearing a (Z)-alkylidenylbenzylsilyl group. A variety of substitution patterns and heteroatom substituents were compatible. These alkylidenylsilanes underwent palladium-catalyzed cross-coupling with aryl iodides promoted by tetra-n-butylammonium fluoride, displaying a broad substrate scope. This catalytic system shows a broad compatibility towards substitution patterns, electronic properties, and heteroatoms. All of the cross-coupling reactions proceeded in high yields under very mild conditions and with complete retention of double bond configuration, resulting in densely functionalized 3-(Z)-benzylidenecyclopentanes and analogous heterocycles. This synthetic method was applied to the total synthesis of a marine natural product of the kanoid family, isodomoic acid H. This total synthesis was achieved via a short twelve step longest linear sequence, in which the key transformations include a diastereoselective rhodium-catalyzed carbonylative silylcarbocyclization reaction of a vinylglycine-derived 1,6-enyne, a desilylative iodination reaction with an inversion of double bond configuration, as well as an alkenyl-alkenyl silicon-based cross-coupling reaction uniting the core alkenyl iodide and the side-chain silanol. The mechanistic insight garnered during the investigation of the invertive desilylative iodination reaction enabled the accomplishment of a desilylative iodination reaction with an inversion of double bond configuration, thus opening up a promising synthetic route leading towards the total synthesis of isodomoic acid G, a congener of isodomoic acid H. Made available in DSpace on 2015-09-25T22:14:03Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3392195.pdf: 4513508 bytes, checksum: 9468bfae2ec56e8cf2344f30825afa1b (MD5) Previous issue date: 2009 Embargo set by: Seth Robbins for item 85627 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 351 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2009. http://hdl.handle.net/2142/84346 (MiAaPQ)AAI3392195 eng Chemistry, Organic The Development of Sequential Silylcarbocyclization Silicon-Based Cross -Coupling Reactions and Their Application in the Total Synthesis of Isodomoic Acid H text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.