Synthetic routes towards chiral calix[4]resorcinarenes

This thesis is divided into three chapters. Chapter 1 contains a brief overview of the literature reports in the area of calix[4]resorcinarene chemistry. The many methods available for the preparation and use of these macrocycles, their functionalisation on both the upper and lower rims and the use of Mannich reaction protocols for the introduction of chirality into these symmetrical molecules are discussed. Chapter 2 describes new methodology for the formation of a range of chiral calix[4]resorcinarenes, most notably the formation of tetra alkyloxy calix[4]resorcinarenes as racemic mixtures, which can then be separated as diastereoisomers following the use of new Mannich reaction methodology for the formation of tetra benzoxazine derivatives. One of these enantiomerically pure resorcinarenes has been used as a catalyst in the addition of diethylzinc to benzaldehyde. The attempts made at deepening the cavity of these macrocycles, by utilising Sonogashira coupling reactions, are also discussed. Chapter 3 contains the experimental details and analytical data for the successful reactions discussed in Chapter 2

The desymmetrisation of resorcinol: The synthesis of resorcinol monoalkyl ethers

The desymmetrisation of resorcinol to give 3-alkoxyresorcinol derivatives can be achieved in excellent yields either from resorcinol monobenzoate and alcohols using Mitsunobu reactions followed by hydrolysis using a strong base or by using 3-iodophenylbenzyl ether as a resorcinol monobenzyl ether equivalent in reactions with alcohols catalysed by copper(I)-9,10-phenanthroline followed by ammonium formate-palladium catalysed hydrogenolysis