Nickel-catalyzed arylative cyclizations enabled by reversible alkenylnickel E/Z isomerization

Yap, Connor (2019) Nickel-catalyzed arylative cyclizations enabled by reversible alkenylnickel E/Z isomerization. PhD thesis, University of Nottingham.

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Herein is described the first enantioselective intramolecular allylation of alkenylnickel nucleophiles. These reactions are initiated by the addition of an arylboronic acid across an alkyne, followed by cyclization of the resulting alkenylnickel species onto an allylic phosphate. The reversible E/Z isomerization of the alkenylnickel species is essential for the success of the reactions.

This process delivers chiral 1,4-diene-containing hetero- and carbocycles, previously inaccessible via established rhodium catalysis, with excellent levels of regio- and stereocontrol. This reaction further demonstrates the power of reversible alkenylnickel E/Z isomerization in providing products that would otherwise be inaccessible using syn-selective alkyne carbometallation processes.

Attempts to extend this reactivity to other classes of electrophilic traps are also described.

Item Type: Thesis (University of Nottingham only) (PhD)
Supervisors: Lam, Hon Wai
Keywords: Enantioselective intramolecular allylation; Alkenylnickel nucleophiles
Subjects: Q Science > QD Chemistry
Faculties/Schools: UK Campuses > Faculty of Science > School of Chemistry
Item ID: 55829
Depositing User: Yap, Connor
Date Deposited: 17 Jul 2019 04:40
Last Modified: 15 Nov 2023 13:19

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