Rhodium-catalysed C-H and C-C bond activation towards the formation of medium-sized rings

Crépin, Damien (2011) Rhodium-catalysed C-H and C-C bond activation towards the formation of medium-sized rings. PhD thesis, University of Liverpool.

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Abstract

Rhodium-catalysed hydroacylation is an elegant methodology which affords ketones in an atom-economical fashion. In this manuscript, the rhodium-catalysed intramolecular hydroacylation of aldehyde-tethered alkylidenecyclopropanes, alkylidenecyclobutanes or alkylideneazetidines is described. This rearrangement which includes a first step of carbon-hydrogen bond activation, a hydrometallation step followed by a ring enlargement and a final reductive elimination of the metal catalyst, leads to the formation of cycloheptenones and cyclooctenones in good to excellent yield. In chapter 1, an overview of the literature on rhodium-catalysed hydro acylation is described. In chapter 2, our efforts to optimise the catalytic conditions and build the scope of 7-membered rings are reported while chapter 3 outlines the results of the mechanistic investigations carried out with aldehyde-tethered alkylidenecyclopropanes. The formation of 8-membered rings is described in chapter 4 and chapter 5 is devoted to the study on the regioselectivity of the ring opening of cyclobutane moieties.

Item Type:	Thesis (PhD)
Depositing User:	Symplectic Admin
Date Deposited:	19 Oct 2023 17:54
Last Modified:	19 Oct 2023 17:58
DOI:	10.17638/03174305
Copyright Statement:	Copyright © and Moral Rights for this thesis and any accompanying data (where applicable) are retained by the author and/or other copyright owners. A copy can be downloaded for personal non-commercial research or study, without prior permission or charge
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3174305