Exploring nucleophilic nitrenoid reactivity to access complex imidazoyl heterocycles

Martínez Arce, Elsa (2019). Exploring nucleophilic nitrenoid reactivity to access complex imidazoyl heterocycles. University of Birmingham. Ph.D.

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Abstract

This thesis describes advances within the field of nucleophilic nitrenoids, with particular focus on the intermolecular reaction of N-pyridinium aminides alongside ynamides and thioynamides, in a gold-catalysed formal [3+2] cycloaddition reaction. The generality of this transformation is demonstrated with the construction of highly functionalised 5,5,6-, 5,5- and 5,6-fused imidazolyl derivatives.

Five new types of N-pyridinium aminides bearing a benzothiazole, benzoxazole, thiazolone, imidazolone and pyrimidinone core, have been synthesised. Their preparation, scope and limitations across a variety of ynamides in the gold-catalysed cycloaddition is discussed, along with mechanistic insights.

Thioynamides are presented as priviledge ynamides for the gold-mediated annulation reaction. Their use can overcome challenging reactivity observed within some of the nitrenoid series. The prominent improvement regarding the aminide scope is shown. Preliminary investigations into an unprecedented sulfur effect displayed by these N,S-substituted alkynes and the proposed mechanistic rationale of that enhancement are discussed.

Type of Work:	Thesis (Doctorates > Ph.D.)
Award Type:	Doctorates > Ph.D.
Supervisor(s):	Supervisor(s) Email ORCID Davies, Paul UNSPECIFIED UNSPECIFIED Simpkins, N. S. UNSPECIFIED UNSPECIFIED Lamont, Scott UNSPECIFIED UNSPECIFIED
Licence:	All rights reserved
College/Faculty:	Colleges > College of Engineering & Physical Sciences
School or Department:	School of Chemistry
Funders:	None/not applicable
Subjects:	Q Science > QD Chemistry
URI:	http://etheses.bham.ac.uk/id/eprint/10139

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