Enzymatic Studies of Bromocyclohexadienediols & Semi-synthesis of Narciclasine Analogues

Abstract

This thesis describes two projects: • cis-Diene bromo diol obtained from the microbial oxidation of bromobenzene was used as a substrate for lipase-catalyzed acylation and epoxidation reactions. The model studies showed that the regiochemistry of the acylation is solvent dependent. The chemoenzymatic epoxidation followed the expected regiochemistry when compared to the chemical epoxidation with m-CPBA, but with the unexpected formation of bromoconduritol-C, an important intermediate whose electrochemical reduction led to the short synthesis of (-)-conduritol-C. • A detailed description is given to the studies of conversion of natural narciclasine to its C-1 enol derivative, followed by the attempted conversion of this material to its triflate, in order to conduct cross-coupling at the C-1 position. However, it resulted in a triflate at C-6 that was successfully coupled with several functionalities. All compounds were fully deprotected and subjected to evaluation of biological activity. Only one derivative showed moderate activity as compared to those of narciclasine and pancratistatin. Spectral and physical data are provided for all new compounds.