Rapid increase of molecular complexity through C–H and C–C bond activation

Ho, Kelvin
Rapid increase of molecular complexity through C–H and C–C bond activation. PhD thesis, University of Liverpool.

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The activation of carbon-hydrogen (C–H) and carbon-carbon (C–C) bonds by transition metal catalysts is an attractive strategy to streamline organic synthesis. Herein this manuscript, the two main areas of research are described. Firstly, it was found that a nickel catalyst can promote the insertion of alkynes into the C–C bond of 3-azetidinones and 3-oxetanones to enable quicker access to pyranones and pyridinones in high yields and excellent regioselectivity. Secondly, a rhodium-catalysed pyridine directed C–H bond activation enables the rearrangement of 1,6-heptadienes into bicyclo[2.2.1]heptanes in good yields. Importantly, three stereogenic centres are created with complete diastereocontrol in this atom-efficient reaction. In chapter 1, an overview of the literature on transition metal-catalysed C–C bond activation of four membered rings is described. In chapter 2, our efforts to optimise the catalytic conditions and build the scope of the nickel-catalysed reaction are reported. In chapter 3, the results of the mechanistic investigations of the nickel-catalysed reaction are reported. Finally in chapter 4, a brief overview of the transition metal-catalysed functionalisation of an alkene C–H bond with another alkene is described. Subsequently, the optimisation of the catalytic conditions and the scope of the diastereoselective carbocyclisation of 1,6-heptadienes triggered by rhodium-catalysed activation of an alkene C–H bond are reported.

Item Type: Thesis (PhD)
Additional Information: Date: 2014-09 (completed)
Subjects: ?? QD ??
Depositing User: Symplectic Admin
Date Deposited: 08 Sep 2015 14:38
Last Modified: 17 Dec 2022 00:49
DOI: 10.17638/02006222
URI: https://livrepository.liverpool.ac.uk/id/eprint/2006222