Development of Oxidative Coupling Reactions for the Total Synthesis of Natural Products

Through the use of oxidative coupling reactions, new synthetic methods for direct carbon-carbon bond formation can be developed to enable the streamlined syntheses of complex molecules. This under-explored class of reactions is proposed to proceed through a single-electron transfer mechanism, and can allow for the construction of bonds between unfunctionalized carbon atoms; an incredibly powerful tool in synthetic chemistry.;This work has sought to continue exploring the use of silicon tethers to afford new methods for the cross-coupling of compounds through oxidative carbon-carbon bond formation. Through the development of such chemistry, this work has led to the total synthesis of propolis-benzofuran B and butylcycloheptylprodigiosin (BCHP), as well as a new method for the oxidative allylation of ketones.;By completing the synthesis of BCHP we were able to determine that it is not a natural product, but a missassigned structure of streptorubin B. This has given rise to a biosynthetic hypothesis for the evolution of cyclic prodigiosins. We have initiated studies of our synthetic prodigiosins to further validate this hypothesis and purpose for the cyclic prodigiosin alkaloids.