Sulfur-containing heterocycles are currently attracting a great deal of interest in several diverse fields. For instance, substituted tetrahydrothiophenes have received considerable attention due to their extremely wide-ranging chemical and biological applications. These include their use as potent a-glucosidase inhibitors, as an inhibitor of copper amine oxidases and as selective A3 agonists and antagonists. In addition, they have been utilised in chemical transformations, such as catalytic asymmetric epoxidation, catalytic intramolecular cyclopropanation, and asymmetric metal catalysis hydrogenation. From a nanochemical perspective, the adsorption chemistries and physical properties of various thiophenes and tetrahydrothiophenes on gold surfaces have recently come to the fore. Polythiophenes are also key compounds in modern materials research, currently utilised in, for example, the fabrication of semi-conducting, fluorescent, and electronic and optoelectronic materials.In this work, metallation (exchange of a hydrogen atom with a metal atom) of the parent heterocycles, tetrahydrothiophene (THT) and thiophene is considered. Metallation is one of the most fundamental reactions in modern day synthesis and is a key tool in the preparation of functionalised aromatic and heterocyclic compounds. It is usually achieved by the utilisation of commercially accessible organolithiums (or lithium amides); however, these reactions do have their drawbacks, including the intolerance of certain functional groups, the need for cryoscopic temperatures and the inadvertent reactivity with polar reaction solvents.