Home Products Cited in Publications Worldwide Sustainable methodologies for synthesis of small organic molecules using micellar catalysis
University of Louisville,2024,4274.
Deborah Sam Ogulu
Organic synthesis is a critical process in the creation of small molecule pharmaceuticals and agrochemicals. However, most methods for synthesizing these small molecules rely on toxic organic solvents as the reaction medium which account for approximately 80% of pharmaceutical waste. Moreover, many catalytic reactions require expensive endangered precious metals like palladium and costly metals. This dissertation presents research that aims to develop sustainable, eco-friendly reaction conditions to address these issues. Chapter 1 provides an overview of green and sustainable chemistry and chemistry in water. It explains what sustainability entails and the drive towards greener synthetic methods. Also included is the introduction to the concept of chemistry in water, the different types of roles of water in chemistry, and the development of micellar catalysis – including its evolution, applications, current challenges, and future directions. Chapter 2 discusses the development of a ligand-free bimetallic nanocatalyst for the hydrogenation of unsaturated enones. This ligand-free nanocatalyst was prepared from nickel and ppm loading of palladium and was stabilized by harnessing the structural features of the amphiphile, PS-750-M. The physical properties of the nanoparticles were evaluated and thoroughly characterized using different analytical techniques like HRTEM, XPS, and TGA. Chapter 3 describes the application of a copper catalyst in the hydroboration of unsymmetrical internal alkynes with high regioselectivity under aqueous micellar conditions. The methodology was amenable to internal alkynes with diverse functional groups and provides a unique route to access β selective alkenyl boronates. Chapter 4 showcases the development of a protocol towards coupling of aryl boronic acids and primary amines under aqueous micellar conditions using an inexpensive nickel catalyst and oxygen balloon. The developed methodology provides another way to access amines under more sustainable reaction conditions. Chapter 5 describes the use of ppm palladium and copper catalysts immobilized on silica for the catalytic dehydration of amides to nitriles. The protocol employs acetonitrile as the additive and the reaction is performed using aqueous PS-750-M as the reaction medium.