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Callingham, Michael (2018) Reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations. PhD thesis, University of Nottingham.

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Abstract

Herein is described the catalytic in situ generation of nucleophilic allylmetal species through the activation of allylic C-H bonds. Reactivity is achieved through initial carbometalation of an enyne, followed by the key 1,4-alkenyl-to-allyl metal migration which generates the allylmetal intermediate.

This new mode of reactivity was firstly employed in the rhodium-catalysed diastereoselective reaction of arylboron reagents with enynones, to give products containing three contiguous stereocentres. Initial discovery and optimisation of this reaction was performed by Benjamin Partridge. Through use of a chiral sulfur olefin ligand, products could be obtained in high enantioselectivites.

Secondly, a three-component coupling between 1,3-enynes, arylboronic acids and imines is described. The use of a chiral rhodium catalyst allowed the synthesis of a range of homoallylic amines with excellent control of stereoselectivity (>95:5 dr, up to 99% ee).

Item Type:	Thesis (University of Nottingham only) (PhD)
Supervisors:	Lam, Hon Wai Dowden, J.
Subjects:	Q Science > QD Chemistry > QD241 Organic chemistry
Faculties/Schools:	UK Campuses > Faculty of Science > School of Chemistry
Item ID:	52053
Depositing User:	Callingham, Michael
Date Deposited:	17 Aug 2018 14:40
Last Modified:	19 Jul 2020 04:30
URI:	https://eprints.nottingham.ac.uk/id/eprint/52053

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