Enantioselective Nickel-Catalysed Arylative and Alkenylative Cyclisations onto Electron-Deficient Alkenes via E/Z Isomerisation
Publication Date
July 26, 2023
Creator
Abstract
Herein is presented a highly enantioselective nickel-catalysed anti-carbometallative-cyclisation reaction of substrates containing an alkyne tethered to an electron-deficient alkene. Enantioenriched cyclopentene products, that are otherwise difficult to synthesise, are obtained in up to 99% yield and >99% ee. The overall anti-carbometalation of the alkyne is enabled by the critical reversible E/Z isomerisation of alkenylnickel intermediates.
Investigation of the substrate scope revealed that alkyne substituents such as (hetero)aryl and alkenyl groups were compatible with the reaction and substrates containing electron-deficient alkenes such as α,β-unsaturated alkyl or (hetero)aryl ketones, nitroalkenes, α,β-unsaturated esters and alkenyl nitriles successfully participated in the reaction. Also, (hetero)arylboronic acid as well as alkenylboronic acids were tolerated in the reaction.
Efforts were made towards the synthesis of enantioenriched 6-membered carbo- and heterocyclic products by extending the tether between the alkyne and the electron-deficient alkene in the substrate.
Item Type
ethesis
Thesis Type
PhD
Supervisors
Subjects (LC)
Associated Schools / Departments
School of Chemistry
eprints ID
73697
UoN Repository URI
Except where otherwise noted, this item's license is described as
File(s)![Thumbnail Image]()
Name
PhD Thesis - Simone Gillbard Corrected.pdf
Type
Full-text
Description
Examined. Corrected Thesis
Size
11.21 MB
Format
Adobe PDF
Checksum (MD5)
57a788574c39b286da72ab3ea59136a8