University of Edinburgh
Joseph Black Building
David Brewster Road
0131 650 4795
The profound impact of organometallics on modern synthetic organic chemistry is indisputable. One of the key aims of the group is to use mechanistic insight (gained through a variety of modern physical-organic/inorganic techniques) to advance further the utility and application of organometallics - both as stoichiometric reagents and as catalysts – in synthetic organic chemistry. As such, we engage in a diverse range of activities in areas that include physical-organic chemistry, organic synthesis, organometallic and coordination chemistry.
We have made a number of fundamental contributions to the understanding of the mechanism by which main group reagents and homogeneous catalysts function, frequently resulting in the replacement of deep-seated mechanistic or structural dogma with simpler and more coherent explanations. Examples organtrifluoroborate solvolysis and coupling, asymmetric induction by the Trost ligand, ethylene acceleration in enyne metathesis, stereochemical pathways in Mo-catalysed allylation, and autocatalysis in the Baylis-Hillman reaction.
In parallel with this work we have applied mechanistic elucidation in the informed design and development of reactions and processes of utility to the synthetic chemist in academia and in the pharmaceutical and agrochemical industries.
Prime examples include a gold-catalysed direct arylation, a new reaction pathway for acceleration of amide solvolysis, ligand design for unprecedented enantioselectivity in imine allylation, the first catalysed diamination of alkenes, and new techniques for testing chiral catalysts in racemic form.
Transmetallation in Suzuki-Miyaura Coupling: The Fork in the Trail, Alastair J. J. Lennox and Guy C. Lloyd-Jones*, Angew. Chem. Int. Ed. 52, 7362-7370, 2013
Gold-Catalyzed Direct Arylation, Liam T Ball, Guy C Lloyd-Jones* and Christopher A. Russell*, Science, 337, 1644-1648, 2012
The Mechanism of Metal-Free Hydrogen Transfer Between Amine-boranes and Aminoboranes, E. Leitao, N. Stubbs, A. Robertson, H. Helten, R. J. Cox, G. C. Lloyd-Jones,* and I. Manners*, J. Am. Chem. Soc., 134, 16805-16816, 2012
Organotrifluoroborate Hydrolysis: Boronic Acid Release Mechanism and an Acid-Base Paradox in Cross-Coupling, Alastair J. J. Lennox and Guy C. Lloyd-Jones*, J. Am. Chem. Soc., 134, 7431-7441, 2012
Development of a generic mechanism for the dehydrocoupling of amine–boranes: a stoichiometric, catalytic and kinetic study of H3B•NMe2H using the [Rh(PCy3)2]+ fragment, Laura J. Sewell, Guy C. Lloyd-Jones* and Andrew S Weller*, J. Am. Chem. Soc., 134, 3598-3610, 2012
Switching Pathways: Room Temperature Neutral Solvolysis and Substitution of Amides, Marc Hutchby, Chris E. Houlden, Mairi F. Haddow, Simon N. G. Tyler, Guy C. Lloyd-Jones,* and Kevin I. Booker-Milburn*, Angew. Chem. Int. Ed., 51, 548-551, 2012
The Even-Handed Approach: Strategies for the Deployment of Racemic Chiral Catalysts, Louise A. Evans, Neil S. Hodnett and Guy C. Lloyd-Jones*, Angew. Chem. Int. Ed., 51, 5126-5133, 2012
[(RCN)2PdCl2]-Catalyzed E/Z Isomerization of Alkenes: a Non-Hydride Binuclear Addition-Elimination Pathway, Emily H. P. Tan, Guy Lloyd-Jones,* Jeremy N. Harvey,* Alastair J. J. Lennox and Benjamin M. Mills, Angew. Chem. Int. Ed., 50, 9602-9606, 2011