Reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations
Publication Date
July 19, 2018
Creator
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
ethesis
Thesis Type
PhD
Supervisors
Subjects (LC)
Associated Schools / Departments
School of Chemistry
eprints ID
52053
UoN Repository URI
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Name
Michael Callingham - Corrected Thesis.pdf
Type
Full-text
Description
Examined
Size
12.92 MB
Format
Adobe PDF
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