The Greaney group works in organic chemistry, developing new methods that enable faster, cleaner and better synthesis. Principal research themes are: 1) Metal-free arylation; 2) integrated bio- and chemo-catalysis; 3) transition metal catalysed C-H activation.
Metal-free arylation
We are interested in establishing alternatives to precious metal-catalysed arylation that can define new disconnections and offer more sustainable chemistries for arene production. Our primary focus is on sulfonamides and arynes as arylating agents; sulfonamides are readily available building blocks that can act as nucleophilic arene donors through desulfonylative Smiles rearrangement processes, whilst the rich chemistry of arynes is driven by the electrophilicity of the strained triple bond. Both regimes present opportunities for new reactivity involving single electron (photoredox), polar, and pericyclic approaches
Integrated Catalysis
The Greaney lab has a long-standing interest in the merger of biomolecules, such as proteins, with small molecules in a single reaction system. Our early investigations centred on dynamic covalent chemistry (DCC), using reversible reactions to create assemblies of molecules at equilibrium that were adaptive to proteins. Current projects are focussed on integrated catalysis, where we unify biocatalytic and chemocatalytic processes to achieve transformations that would not be possible under a single catalytic regime. Work with the Micklefield group has integrated biohalogenation with metal-catalysed arylation and cyanation to create new C-H functionalisations, and collaboration with the Turner group has merged gold catalysed C-C bond formation with amine bio-catalysed oxidation.
Transition metal catalysed C-H activation
C-H Activation has had a profound impact on synthetic design and strategy in recent years, enabling C-H bonds formerly considered as inert to undergo C-C and C-X bond forming processes. The gains in efficiency are significant; lengthy pre-functionalisation processes are avoided, shortening routes, reducing costs, and opening up new disconnections to synthesise structures that were previously thought to be inaccessible. We aim to discover new modes of reactivity in C-H activation that achieve regiocontrol, functional group tolerance and enable new bond forming events. Current areas of interest include ruthenium catalysis for selective arene C-H activation, photo-metalloredox catalysis, and cascade catalysis. Earlier work from our lab established new decarboxylative C-H activation strategies, on-water conditions for the arylation of heteroarenes that operate under mild reaction conditions, and C-H coupling under palladium catalysis.