Two main research topics are discussed in this thesis: a) the synthesis and reactivity of small and medium size paracyclophanes; b) the synthesis and applications of new classes of chiral macrocycles derived from amino acids. The first chapter is a concise review on the synthesis and use of [2.2]paracyclophane derivatives as ligands in asymmetric catalysis and molecular recognition processes, with particular emphasis on tricarbonylchromium(0) complexes of [2.2]paracyclophane. In the second chapter the synthesis and reactivity of tricarbonyl chromium (0) complexes of small and medium size paracyclophanes towards asymmetric derivatisation is described. Various synthetic systems have been examined in asymmetric deprotonation/quench sequences directed towards obtaining enantio-enriched derivatives by a procedure that would provide an alternative to more classical methods such as enzymatic and chemical resolution. The third chapter is a comprehensive critical review of the applications of chiral macrocycles derived from amino acids in areas as diverse as ion transport across membranes, catalysis, development of new antibiotics and new materials. The fourth chapter describes the synthesis of two new classes of chiral macrocycles via a versatile route, which potentially gives diverse and useful systems. The structure of the synthetic macrocycles, whose chirality is derived from the incorporation of amino acids as building blocks, has been examined by X-ray analysis. This led to the prediction that the presence of hydrogen bond donors and acceptors in the structure of these systems plays an important role in determining the interaction of such macrocycles with guest candidates. This chapter also details a study of the host properties of the synthetic macrocycles towards organic and metal guests. The fifth chapter contains the experimental details of the work described in chapters 2 and 4. The appendix (Chapter 6) contains supporting information for the X-ray analyses performed during the course of the work while Chapter 7 provides the reader with full bibliographic details.