I. synthesis, reactivity, structure and application of spiroepoxy-b-lactones: studies toward (-)-maculalactone a ii. metal mediated couplings of dichloroolefins applicable to the haterumalides
Abstract
Marine natural products have continued to be a source of compounds with
interesting structures and biological activities. Two such compounds are maculalactone
A and haterumalide NA. In the process of exploring a route to the synthesis of
haterumalide NA, the novel ring system, spiroepoxy-b-lactones were discovered.
Spiroepoxy-b-lactones were synthesized by the oxidation of ketene-homo dimers with
dimethyldioxirane (DMDO). After a synthetic route to this ring system was obtained we
next explored the varied reactivity of spiroepoxy-b-lactones, and it was apparent that
they might be applied to the synthesis of maculalactone A.
Also with the aim of the total synthesis of the haterumalides, a palladium
catalyzed cross coupling was developed. This reaction couples a 1,1-dichloroolefin with
an alkyl zinc reagent. It was found that this reaction necessitates a heteroatom on the
zinc reagent in order to proceed.
Citation
Duffy, Richard Jeffrey (2007). I. synthesis, reactivity, structure and application of spiroepoxy-b-lactones: studies toward (-)-maculalactone a ii. metal mediated couplings of dichloroolefins applicable to the haterumalides. Doctoral dissertation, Texas A&M University. Available electronically from https : / /hdl .handle .net /1969 .1 /ETD -TAMU -2444.