Novel Approaches to Catalytic Acyl Transfer Reactions

Abstract

This thesis describes work carried out over the past 3 years towards the development of novel catalytic methods for acyl transfer reactions.

Chapter 1 presents the current industrial and literature methods of forming amide bonds from carboxylic acids and amines. The use of coupling agents and activators is explained in addition to the development of catalytic methods including homogeneous (transition metal, p-block, and non-metals) and heterogeneous methods. Following this, results are presented on improving a previously established catalytic system for the direct coupling of carboxylic acids and amines using zirconocene dichloride. Three methods of achieving this were explored, firstly by addition of a nucleophilic additive, secondly by utilising a more active zirconium catalyst and finally by removing water from the system.

Chapter 2 builds on the material presented in Chapter 1, by exploring the use of alternative acyl donors in the formation of amide bonds. It details the use of esters, carbamates, ureas and amides in amide bond formation and transamidation reactions. The zirconocene dichloride system is then applied to these alternative acyl donors to form amides from esters and substituted ureas from carbamates.

Chapter 3 focusses on the formation of primary amides from carboxylic acids. Recent literature methods towards the synthesis of primary amides are first described, followed by a novel catalytic methodology for the formation of primary amides from carboxylic acids with urea as an ammonia source.

Chapter 4 then provides details of all experimental procedures and characterisation of the compounds that were synthesised.

Date of Award	6 Jun 2015
Original language	English
Awarding Institution	University of Bath
Supervisor	Jonathan Williams (Supervisor) & Steven Bull (Supervisor)