University of North Carolina at Chapel Hill Graduate School
Doi
Abstract
ABSTRACT Megan Elizabeth Schutzbach-Horton: DEVELOPMENT OF PHOTOREDOX CATALYSIS-MEDIATED FUNCTIONALIZATION METHODS FOR ARENES AND OLEFINS (Under the direction of David A. Nicewicz) I. Introduction to Organic Photoredox Catalysis This chapter provides a brief discussion of relevant photophysical properties and the thermodynamics of photoinduced electron transfer. The development of acridinium ion catalysts and their use by our lab is also included. II. Development of Photoredox Catalysis-Mediated Methods for the Hydrofunctionalization of Glycals Efforts to-date on the development of glycal hydrofunctionalization methods using acridinium-mediated photoredox catalysis are summarized. This work includes data obtained by Heqing Sun on the use of exo-glycals as substrates in a hydroalkoxylation reaction. The latter portion of the chapter summarizes efforts towards the use of endo-glycals as substrates in a variety of hydrofunctionalization methods, including hydroamination and hydroalkoxylation reactions. III. Development of a Photoredox-Mediated Method for the Anti-Markovnikov Hydroazidation of Activated Olefins This chapter discusses the use of acridinium-mediated photoredox catalysis in the development of an anti-Markovnikov hydroazidation method that is complementary to existing work. Using mild conditions that feature the use of TMSN3 and TFE, we report the synthesis of 31 organic azides in yields ranging from 22 – 98%. IV. Development of a Method for the Nucleophilic Defluorination of Electron-Neutral and Electron-Rich Fluoroarenes In this chapter, the development of a general method for the use of electron-neutral and electron-rich fluoro(hetero)arenes as substrates in a CRA-SNAr reaction is discussed. Using both an acridinium catalyst, as well as a novel xanthylium catalyst, conditions were developed for 78 examples of nucleophilic defluorination in a manner that is complementary to existing SNAr chemistry.Doctor of Philosoph
