New reactive sites enabled via an allyl-to-allyl 1,4-Rh(III) migration

Korkis, Stamatis E. (2018) New reactive sites enabled via an allyl-to-allyl 1,4-Rh(III) migration. PhD thesis, University of Nottingham.

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Abstract

The Rh(III)-catalysed oxidative C–H allylation and homoallylation of N-acetylbenzamides with 1,3-dienes is described. The presence of allylic hydrogens cis to the less substituted alkene of the 1,3-diene is important for the success of these reactions, though not essential. With the assistance of reactions using deuterated 1,3-dienes, a proposed mechanism is provided. The key step is postulated to be the first reported examples of allyl-to-allyl 1,4-Rh(III) migration. Importantly, migration to primary or secondary allylic position results in allylation products, whereas migration to a tertiary position leads to homoallylation. Using 1,4-dienes as the coupling partner, N-tosylbenzamides are homoallylated. Preliminary results indicate a mixture of isomer products, with major isomer resulting from an allyl-to-allyl 1,4-Rh(III) migration.

Item Type: Thesis (University of Nottingham only) (PhD)
Supervisors: Lam, Hon Wai
Denton, R.
Keywords: Rh(III)-catalysis, directed and remote C-H functionalisation, 1,4-migration, 1,4-allylic transposition, chain-walking, allylic isomerisation, β-hydride elimination
Subjects: Q Science > QD Chemistry > QD241 Organic chemistry
Faculties/Schools: UK Campuses > Faculty of Science > School of Chemistry
Item ID: 48787
Depositing User: Korkis, Stamatis
Date Deposited: 15 Mar 2018 04:40
Last Modified: 16 Mar 2018 15:42
URI: http://eprints.nottingham.ac.uk/id/eprint/48787

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