Studies towards enantioselective metal-catalysed nucleophilic allylations using allenes

Di Sanza, Riccardo (2020) Studies towards enantioselective metal-catalysed nucleophilic allylations using allenes. PhD thesis, University of Nottingham.

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Abstract

The enantioselective intramolecular nickel-catalysed nucleophilic 1,2-allylation of ketones with (hetero)arylboronic acids or potassium vinyltrifluoroborate and progress towards the enantioselective intramolecular 1,4-allylation of enones with dialkylzinc nucleophiles are described. The first project is initiated by carbonickelation of allenes which gives the nucleophilic allylnickel species that cyclise by 1,2-allylation onto a tethered ketone to produce a range of chiral tertiaryalcohol containing aza- and carbocycles in excellent diastereo- and enantioselectivities. The second project is initiated by the oxidative cyclisation of Pd(0) with an allene tethered to an enone. The resulting palladacycle formed undergoes transmetalation with a dialkylzinc nucleophile, and subsequent reductive elimination affords 6,5-fused bicycles in high diastereoselectivity.

Item Type: Thesis (University of Nottingham only) (PhD)
Supervisors: Lam, Hon Wai
Ball, Liam
Keywords: Chiral pyrrolidin-2-ones; Nucleophilic allylation; Tertiary alcohol; Ketones; High enantioselectivity; Nickel catalysis
Subjects: Q Science > QD Chemistry
Faculties/Schools: UK Campuses > Faculty of Science > School of Chemistry
Item ID: 59565
Depositing User: Di Sanza, Riccardo
Date Deposited: 03 Jun 2020 12:35
Last Modified: 03 Jun 2020 12:45
URI: http://eprints.nottingham.ac.uk/id/eprint/59565

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