Reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations

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 Aug 2018 18:45
URI: http://eprints.nottingham.ac.uk/id/eprint/52053

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