MSci, DPhil, MRSC
- +44 (0)131 451 8071
William Perkin Building
Organic Synthesis and Catalysis
Our research is aimed at developing new methods for stereoselective synthesis. These include the use of catalysis for key bond-forming reactions. We are also involved in a number of collaborative projects, in particular with physical chemists, studying interactions of light with small molecular systems.
1. Catalytic C-N bond formation
There is an ongoing need for milder methods for the formation of carbon-nitrogen bonds. We have recently discovered a new synthesis of cyclic sulfamidates by intramolecular allene hydroamination, allowing access to a range of functionalised amines, including those with challenging N-susbtituted quaternary centres. We are currently examining the extension of this process to other related compounds.
Figure 1. Gold(I)-catalysed sulfamidate formation.
2. Synthetic and computational studies on furan cycloadditions
Intramolecular cycloadditions are among the most powerful methods for the formation of polycyclic systems. In collaboration with the Prof. Martin Paterson, we have been investigating substituent (in particular, halogenation and nitration) effects on furan cycloadditions. We have demonstrated a correlation between theory and experiment and have discovered some unusual counter-intuitive behaviour in these systems..
Figure 2. Substituent effects on intramolecular cycloadditions.
3. New aromatic macrocycles for two-photon absorption
Compounds which can simultaneously absorb two photons of light have the potential for a range of applications in biology in medicine. Porphycenes are porphyrin isomers which have been identified as having particularly promising two-photon absorption (TPA) properties. We are currently examining the effect of substitution and core electronics on TPA.
Figure 3. Porphycenes for Two-Photon Absorption.
1. T. Cowie, L. C. Kennedy, J. M. Żurek, M. J. Paterson and M. W. P. Bebbington “Crossed McMurry coupling reactions for porphycenic macrocycles: selectivity and rationalization” Eur. J. Org. Chem., 2015, 3818-3823.
2. M. C. M. Higginbotham, A. Troester, A. G. Lindsay, L. C. Kennedy and M. W. P. Bebbington, “Gold(I)-catalyzed synthesis of cyclic sulfamidates: current scope, stereochemistry and competing cycloisomerization” Tetrahedron, 2015, 71, 727.
3. J. M. Żurek, R. L. Rae, M. J. Paterson and M. W. P. Bebbington, “Unusual structure-energy correlations in intramolecular Diels-Alder Transition States”, Invited special issue on cycloaddition chemistry, Molecules, 2014, 19, 15535.
4. R. L. Rae, J. M. Żurek, M. J. Paterson and M. W. P. Bebbington, “Halogenation Effects in Intramolecular furan Diels-Alder reactions: broad scope synthetic and computational studies” Org. Biomol. Chem., 2013, 11, 7946.
5. M. Higginbotham and M. W. P. Bebbington, “Gold(I)-catalysed synthesis of cyclic sulfamidates by intramolecular allene hydroamination” Chem. Commun., 2012, 7565.