Date of Award
Doctor of Philosophy
George A. Kraus
Aconitine, atisine and garrya type diterpene alkaloids show remarkable biological activity and have a number of structural features in common. Due to their complex structure, there is a discrepancy between progress made lately in the identification, isolation and characterization of new members of this family, on one hand, and successful efforts towards their total synthesis, on the other;Our synthetic studies led us to develop a highly reproducible synthesis of adamantane-containing compounds via the corresponding bridgehead anions;Studies on the application of functionalized bridgehead radicals in natural product synthesis resulted in the development of a versatile, mild and highly tolerant procedure for the generation and trapping of bridgehead radicals. The facile and high yield carbon-carbon bond forming reaction mediated by Co(III) complexes under reductive conditions resulted in a very direct entry into the class of gibberellins, aconitine, atisine and spiramine natural compounds. Our thirteen step sequence to a very advanced intermediate in the atisine and spiramine series, possessing the entire carbon framework and suitable functional groups for further conversion into a variety of naturally occurring compounds in this series proceeds in high overall yield and is industrially attractive. A very advanced intermediate in the synthesis of aconitine alkaloids has been prepared using the same bridgehead radical generation methodology.
Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/
Tiberiu Mircea Siclovan
Siclovan, Tiberiu Mircea, "Synthesis of diterpene alkaloids " (1996). Retrospective Theses and Dissertations. 11488.