Transition Metal-Free Arylation and Heterocycle SynthesisArenes are ubiquitous motifs in both naturally occurring and synthetic functional organic molecules. The investigation of metal-free methodology for the installation of these motifs is important for sustainable development and the discovery of new modes of reactivity.Chapter 1. The preparation of halogenated phenoxathin 10,10 dioxides was ascertained to proceed through fluoride-induced decomposition and subsequent recombination of two molecules of the o-trimethylsilyl(aryl) triflate aryne precursors. Chapter 2. A new mild and metal-free methodology for the transition metal-free preparation of 2-amino biaryls using the benzyne intermediate was established. This proceeds via a desulfonative Truce-Smiles rearrangement of an aryl anion in the key bond-forming step. Chapter 3. The electron-poor S-aryl sulfonamides developed in chapter 2 were explored as reagents for metal-free 1,1- and 1,2-carbonamination. Asymmetric catalysis was also investigated for the preparation of enantioenriched alpha,alpha-disubstituted aryl glycine derivatives. Chapter 4. Some organocatalytic methods for the vicarious nucleophilic substitution of hydrogen were investigated to expand the remit of this classical arylation mechanism.