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Green, Harley (2023) Nickel-Catalysed Arylative Cyclisations of Alkynones & Molecular Editing of Cyclic Ketones. PhD thesis, University of Nottingham.

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Abstract

PART I: NICKEL-CATALYSED ANTI-ARYLMETALLATIVE CYCLISATIONS ONTO KETONES

A highly enantioselective and regioselective nickel-catalysed domino reaction of the addition of boronic acids across an alkyne, followed by subsequent cyclisation onto a ketone is reported. The reversible E/Z isomerization of the alkenylnickel intermediate is key to enable the overall anti-arylmetallative cyclisation. The process affords enantioenriched tertiary-alcohol-containing products of which the ring system is featured in several diarylindolizidine alkaloids.

PART II: MOLECULAR EDITING OF CYCLIC KETONES: C-TO-N ATOM EXCHANGE

A process for the molecular editing of α-substituted cyclic ketones by performing a formal C-to-N atom exchange is reported. The key first step involves ring-opening the ketone, with the ketoacid product being leveraged through a Curtius rearrangement to introduce the nitrogen atom. Finally, a ring closing step forms the C-to-N atom exchanged product. This process involves simple air-tolerant chemistry, and the products themselves can be purified without the need for column chromatography with a preliminary scope of five compounds being reported.

Item Type:	Thesis (University of Nottingham only) (PhD)
Supervisors:	Lam, Hon
Keywords:	alkynes, ketones, alkenes, heterocyclic chemistry
Subjects:	Q Science > QD Chemistry > QD241 Organic chemistry
Faculties/Schools:	UK Campuses > Faculty of Science > School of Chemistry
Item ID:	72269
Depositing User:	Green, Harley
Date Deposited:	31 Jul 2023 04:40
Last Modified:	31 Jul 2023 04:40
URI:	https://eprints.nottingham.ac.uk/id/eprint/72269

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