Small rings are frequently found in natural products as well as incorporated into drugs and agrochemicals in which they impart valuable properties on the biological activity of these compounds. Cyclopropanes are also extremely useful as reagents in organic synthesis, in particular as “umpolung” reagents, allowing access to products which would otherwise be more difficult to synthesise. This thesis will describe forays into the synthesis and further substitution of small rings as well as the iminium-catalysed ring-opening of cyclopropanes. The introduction will outline the uses and properties of cyclopropanes, and will also describe some of the more common ways for incorporating cyclopropanes into larger structures. This will include the Horner–Wadsworth–Emmons procedure which has previously been developed by the group. The second chapter describes efforts towards the iminium-catalysed nucleophilic ring-opening of cyclopropanes. This is followed by Chapter 3, in which the Horner–Wadsworth–Emmons methodology for the synthesis of the cyclopropanes used in Chapter 2 is investigated as a procedure for the synthesis of 4-membered heterocycles. Chapter 4 describes the development of a decarboxylative method for the protodecarboxylation of cyclopropanecarboxylic acids. This was developed as the first step towards decarboxylative cross-coupling of cyclopropanes. Decarboxylative cross-couplings have been extensively developed as environmentally friendly and facile alternatives to the current cross-coupling methods. In Chapter 5 the attempted development of a decarboxylative cross-coupling reaction of cyclopropanes is described. Conclusions and future work are outlined in Chapter 6, followed by the experimental details in Chapter 7.