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Title: Rhodium-catalysed C-H and C-C bond activation towards the formation of medium-sized rings
Author: Crépin, Damien
ISNI:       0000 0004 2732 3272
Awarding Body: University of Liverpool
Current Institution: University of Liverpool
Date of Award: 2011
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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.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available