Date on Master's Thesis/Doctoral Dissertation

5-2024

Document Type

Doctoral Dissertation

Degree Name

Ph. D.

Department

Chemistry

Degree Program

Chemistry, PhD

Committee Chair

Handa, Sachin

Committee Member

Luzzio, Frederick

Committee Member

Balabanoff, Morgan

Committee Member

Gallou, Fabrice

Author's Keywords

Green chemistry; micelles; surfactant

Abstract

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. We developed 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. Furthermore, a methodology for the application of a copper catalyst in the hydroboration of unsymmetrical internal alkynes with high regioselectivity under aqueous micellar conditions was evaluated. The methodology was amenable to internal alkynes with diverse functional groups and provides a unique route to access β selective alkenyl boronates. In addition, a protocol towards the coupling of aryl boronic acids and primary amines under aqueous micellar conditions using an inexpensive nickel catalyst and oxygen balloon was explored. The developed methodology provides another way to access amines under more sustainable reaction conditions. Finally, we describe 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. All the methodologies explored can further be derivatized towards synthesis of pharmaceutically relevant drug intermediates.

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