Exploring the potential of a new linker system cleaved using samarium(II) iodide

Rudkin, Iain (2006) Exploring the potential of a new linker system cleaved using samarium(II) iodide. PhD thesis, University of Glasgow.

Abstract

Exploring the potential of a new linker system cleaved using SmI2. The well known reduction of ?-heterosubstituted carbonyl compounds using SmI2 has been employed in the design for a new linker for phase tag assisted synthesis. Building on work previously reported by the group, the research over the past 3 years has concentrated on increasing the synthetic utility of these new linker systems. The work culminated in what we believe to be the first instance of asymmetry being introduced in the final step of a phase tag assisted synthesis. To illustrate further the potential of the linker system, studies into the synthesis of azepinones, a common structural motif found in many natural products, drugs and their precursors, has been undertaken. Whilst a number of solution phase routes have been developed and optimised, their adaptation to a phase tag synthesis has proved difficult. Nevertheless, the foundations for a feasible route to such targets have been laid. A sequential cleavage-asymmetric protonation strategy has also been developed that allows enantiomerically enriched compounds to be prepared from a phase tag assisted synthesis using our linker design. Chirality is introduced in the final step of the phase tag assisted synthesis via the enantioselective protonation of a samarium(III) enolate formed upon release of substrates from the phase tag. Our studies have resulted in many curious observations regarding the reactivity and behaviour of samarium(III) enolates.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Additional Information: Adviser: David Procter
• Keywords: Inorganic chemistry
• Date of Award: 2006
• Depositing User: Enlighten Team
• Unique ID: glathesis:2006-74076
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 23 Sep 2019 15:33
• Last Modified: 23 Sep 2019 15:33
• URI: https://theses.gla.ac.uk/id/eprint/74076