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Title: Palladium-catalysed carbon-fluorine bond activation of fluoroarenes
Author: Chen, Wenyi
ISNI:       0000 0004 9357 060X
Awarding Body: Imperial College London
Current Institution: Imperial College London
Date of Award: 2020
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This thesis focuses on transforming ‘inert’ C–F bonds in readily available fluorocarbons, specifically fluoroarenes, into reactive C–Al bonds. This is a new chemical transformation which we have named “C–F alumination”. In recent years, C–F bond borylation reactions (i.e. the transformation of C–F to C–B bonds) have been developed to generate reactive synthetic building blocks. Each study published has their own advantages and limitations, therefore, the C–F bond alumination protocol reported herein not only addresses some of these limitations, such as high catalyst loading, it also expands the number of catalytic procedures capable of selectively activating C–F bonds and provides a new entry point to organoaluminiums, known to be versatile intermediates in chemical manufacture. In Chapter one, the state of the art methods for the functionalisation of C–F bonds with main group reagents is presented, this literature analysis is centred on methods that generate reactive chemical building blocks such as organoboranes and organosilanes from fluorocarbons. In Chapter two, the serendipitous discovery of a new palladium catalyst for C–F alumination is reported along with the reaction scope and selectivity for a series of pentafluorobiphenyls and tetrafluorobiphenyls. In Chapter three, the substrate scope is then extended to fluorinated monoarenes, followed by preliminary results on an application of the organoaluminium products in carbon–carbon bond formation by cross-coupling. Finally, in Chapter 4 the plausible mechanisms for sp2C–F and sp2C–H alumination are discussed in detail. Both the chemo and regioselectivity are rationalised and insight is provided into the nature and reactivity of the active catalyst and potential catalyst deactivation pathways.
Supervisor: Crimmin, Mark Sponsor: European Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral