Degree Type

Dissertation

Date of Award

1996

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

George A. Kraus

Abstract

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.

DOI

https://doi.org/10.31274/rtd-180813-10515

Publisher

Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/

Copyright Owner

Tiberiu Mircea Siclovan

Language

en

Proquest ID

AAI9635354

File Format

application/pdf

File Size

106 pages

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