Remote transmission of reactivity in rhodium-catalysed reactions
Publication Date
December 13, 2019
Creator
Abstract
Herein is described the remote transition of reactivity in two different rhodium-catalysed transformations.
The first example utilises the rare migration of an allylrhodium species generated in situ from conjugated dienes along a carbon chain towards tethered functional groups in a process known as allylrhodium chain walking. A remote nucleophilic allylation with an electrophile (aldehydes or imines) gives homoallylic alcohol or amine products in high diastereoselectivities.
The second transformation sees reactivity transmitted through an initial carbometalation of an alkyne followed by the key 1,4˗alkenyl˗to˗aryl migration in the desymmetrisation of tethered cyclic and acyclic alkynones to give cyclisation products with an (E)-1-arylidene-1,2,3,4-tetrahydronaphthalene core. Using a chiral (S)˗DTBM-Segphos® ligand gave the products in high enantioselectivities.
Item Type
ethesis
Thesis Type
PhD
Supervisors
Subjects (LC)
Associated Schools / Departments
School of Chemistry
eprints ID
59280
UoN Repository URI
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Name
Alistair Groves Corrected Final Thesis.pdf
Type
Full-text
Description
Examined
Size
10.59 MB
Format
Adobe PDF
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