Sodium-mediated magnesiation of thiophene and tetrahydrothiophene : structural contrasts with furan and tetrahydrofuran

Blair, Victoria L. and Kennedy, Alan R. and Mulvey, Robert E. and O'Hara, Charles T. (2010) Sodium-mediated magnesiation of thiophene and tetrahydrothiophene : structural contrasts with furan and tetrahydrofuran. Chemistry - A European Journal, 16 (29). pp. 8600-8604. ISSN 0947-6539

[thumbnail of strathprints028043]
Preview
Text (strathprints028043)
strathprints028043.pdf
Accepted Author Manuscript

Download (208kB)| Preview

    Abstract

    Sulfur-containing heterocycles are currently attracting agreat 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 propertiesof various thiophenes and tetrahydrothiophenes on gold surfaces have recently come to the fore.[7] 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.[8]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 aromaticand heterocyclic compounds. It is usually achieved bythe utilisation of commercially accessible organolithiums (or lithium amides); however, these reactions do have theirdrawbacks, including the intolerance of certain functionalgroups, the need for cryoscopic temperatures and the inadvertent reactivity with polar reaction solvents.

    ORCID iDs

    Blair, Victoria L., Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564 and O'Hara, Charles T.;