Regioselective C–H thioarylation of arenes using iron catalysis

Dodds, Amy (2023) Regioselective C–H thioarylation of arenes using iron catalysis. PhD thesis, University of Glasgow.

Abstract

The aim of this PhD was to develop novel methods of C–S bond formation using earth abundant transition metal catalysis. The first project focused on the development of a regioselective, iron(III) triflimide-catalysed C–H thioarylation of electron-rich arenes. The methodology was used to synthesise pharmaceutically relevant aryl sulfur-containing compounds, as well as for the late-stage thioarylation of amino acid derivatives. Kinetic studies were undertaken, demonstrating that Nthiosuccinimides bearing electron deficient arenes undergo thioarylation catalysed by the iron(III) triflimide catalyst, whereas, electron rich N-(arylthio)succinimides react via an autocatalytic mechanism partly promoted by the Lewis basic product.

The second and third projects describe the extension of this methodology for the synthesis of sulfur containing heterocycles. In particular, further optimisation studies identified that the iron(III) triflimide-catalysed thioarylation reaction could be accelerated upon addition of a Lewis base catalyst, resulting in a dual Lewis acid/Lewis base catalytic system. Subsequent copper or palladium mediated C–O or C–N cross-coupling reactions were then employed to synthesise small libraries of phenoxathiins and phenothiazines, respectively.

The final project details the development of a synthetic route towards a new class of fluorescent α-amino acids derived from L-tryptophan, which used the iron(III) triflimide/diphenyl selenide dual-catalysed thioarylation reaction as the key step. A small library of compounds was synthesised, which all displayed promising photophysical properties.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Subjects: Q Science > QD Chemistry
• Colleges/Schools: College of Science and Engineering > School of Chemistry
• Supervisor's Name: Sutherland, Professor Andrew
• Date of Award: 2023
• Depositing User: Theses Team
• Unique ID: glathesis:2023-83739
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 25 Jul 2023 13:14
• Last Modified: 25 Jul 2023 13:16
• Thesis DOI: 10.5525/gla.thesis.83739
• URI: https://theses.gla.ac.uk/id/eprint/83739

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