The Diels-Alder reaction was discovered in 1928 and has become the most efficient and practical method for the synthesis of six-membered carbocyclic and heterocyclic rings. This thesis comprises three chapters of results and discussion with the Diels-Alder reaction as a theme. Chapter 2 details an investigation of endo:exo selectivity in the Diels-Alder reactions of 1,3-butadiene. Chapter 3 explores aspects of the intramolecular Diels-Alder reactions of some substituted 1,3,8-nonatrienes, and Chapter 4 describes the domino Diels-Alder reactions of 1,4-diiodo-1,3-butadiene. The Diels-Alder reaction is powerful, general, and widely used in chemical synthesis, and it is well known that many Diels-Alder reactions exhibit endo selectivity, in accord with Alder's empirical rule. The origins of endo:exo selectivity in the Diels-Alder reaction, however, are not completely understood and there is a dearth of experimental evidence concerning the Diels-Alder reactions of the archetypal 1,3-diene, 1,3-butadiene. Chapter 2 describes a study of the Diels-Alder reactions of an isotopically labelled 1,3-butadiene with a range of simple dienophiles, allowing the endo:exo selectivities of these important reactions to be determined for the first time. The experimental data shed light on the origins of endo:exo selectivity in the Diels-Alder reaction and will serve as an important reference for future computational investigations in this area. The intramolecular Diels-Alder reaction shares many of the virtues of its intermolecular counterpart, however its use in chemical synthesis is limited because intramolecular Diels-Alder reactivity and stereoselectivity are often governed by subtle factors, and can be very difficult to predict. As part of a comprehensive experimental and computational collaboration, Chapter 3 describes an investigation of the heat and Lewis acid promoted intramolecular Diels-Alder reactions of some ether tethered 1,3,8-nonatrienes. Also presented are the results of a rate study and a kinetic isotope effect study involving the intramolecular Diels-Alder reactions of some 1,3,8-nonatrienes. The experimental data are analysed and compared with predicted stereoselectivities, activation barriers and kinetic isotope effects obtained from computational modelling. Increased efficiency in chemical synthesis conserves resources, reduces waste, and saves time and money. Domino reactions are particularly efficient processes, which can generate complex products from simple reactants. Chapter 4 describes an investigation of the domino Diels-Alder reactions of (1E,3E)-1,4-diiodo-1,3-butadiene with maleimide dienophiles, through which a family of bicyclo[2.2.2]oct-2-ene derivatives are produced in one high yielding and stereoselective synthetic step.