Development of Sustainable Catalytic Systems For Oxidation Reactions

Abstract

Oxidations are a fundamental class of reactions in organic chemistry.Furthermore, the ability to carry out such transformations in an efficient and selective manner has the potential for widespread application in the production of both bulk and fine chemicals, pharmaceuticals, agrochemicals and many more. Despite this, oxidations are often avoided due to the environmental and economic problems associated with traditional, stoichiometric oxidising agents. Within this thesis, three methods for the aerobic catalytic preparation of carbonyl compounds will be studied. This is done with the aim to develop sustainable methods for aerobic catalytic oxidation reactions that may help in the efforts to use aerobic catalysis on an industrial scale. Chapter two focuses on the development of a metal-free aerobic catalytic system for alcohol oxidation using sterically unhindered nitroxyl radicals in combination with nitric acid. The aim is to broaden the substrate scope of the reaction, whilst using a cheap, abundant source of NOx. Chapter three explores the use of Pd(II) catalysed oxidative carbonylation for the synthesis of 2-alkynoates. The focus is to use lower catalyst loadings than previously reported through the use of ligands, whilst improving the selectivity and substrate scope of the reaction.Chapter four studies Pd(II) catalysed aminocarbonylation for the synthesis of2- ynamides. This system employs a greener solvent, and operates under safer reaction conditions than existing literature, yet maintains equal efficiency and substrate versatility.

Date of Award	Apr 2017
Original language	English
Awarding Institution	Queen's University Belfast
Supervisor	Mark Muldoon (Supervisor)