Synthetic organic chemistry continues to be a driver in the discovery and development of new molecules for applications in biology, medicine, crop science, polymer science, and materials science. Central to the continued development of this field is the pursuit of new strategies and methods for the efficient construction of molecules with precise chemical and structural control. Towards this end, a major focus is the development of catalytic systems to enhance efficiency and specificity. This thesis describes the total synthesis of the complex flavanolignan natural product isosilybin A and the development of new inverse polarity operators. The first Chapter overviews approaches to the synthesis of pyran natural products and details the first stereoselective synthesis of a member of the silybin natural product family, (–)-isosilybin A using a nature-inspired catalytic cyclization. The second Chapter details our efforts towards new open-shell inverse polarity operators. Described is the use of photoredox catalysis to reductively turn electron acceptors, enones and carbonyls, into stabilized radical anions for carbon-carbon bond-forming reactions. Finally, Chapter Three describes our investigation of the 1,2-Brook rearrangement as an approach towards carbonyl nucleophile equivalents by harnessing the unique reactivity of organosilicon compounds.

Last modified

• 11/19/2019

Creator

• Benjamin McDonald

DOI

• https://doi.org/10.21985/n2-gz75-8a55

Subject

• Chemistry

Keyword

• Radical Coupling
• Umpolung
• Brook Rearrangement
• Silymarin
• Photoredox
• Photocatalysis

Date created

• 2018-01-01

Resource type

• Dissertation

Rights statement

• In Copyright