Organometallics in organic synthesis
The Stephenson research group is a leader in the field of organoiron mediated organic synthesis, in which the powerful control effects of carbonyliron complexes are brought in to play several times during a synthesis to get complete control of relative and absolute stereochemistry. Major achievements in recent years have the establishment of general regiocontrolled methods to prepare aryl, alkenyl and alkynyl-substitituted cyclohexadienyliron complexes, and new method to enantiomerically pure complexes by the controlled complexation chiral diene ligands available by biotransformations.
Recent industrial support (Industrial Case Award from GSK) has allowed a detailed investigation of dynamic kinetic resolution effects in asymmetric Heck coupling. A strength of the research on organometallics in organic synthesis in Norwich is the capability to address both stoichiometric and catalytic methods.
Current research is supported through the UEA DTA account (studentship to C. Roe) for an organoiron-mediated synthesis of the alkaloid maritidine.
Organometallic bioprobes
The IR vibrational spectra of carbonylmetal complexes are very sensitive to the local environment of the vibrating M-C=O unit, and this has made possible a novel approach to the design of molecular sensors which takes advantage of the narrow band width of the signals to make multiple measurements in a single experiment. IR-based determinations of pH, Li+/Na+/K+ ratios, π-stacking effects, and protonation/deprotonation events on protein surfaces, have all been established in this work.
Current research is supported in part by the UEA international fund (overseas PhD student: S SudhakaranPillai) and applies these methods to the IR-based detection of sugars and oligosaccharides.
Organometallics for nonlinear optics
The use of organometallics as polarising groups in nonlinear optics has been a collaborative venture coordinated by Stephenson in Norwich through EU COST D4, TMR, COST and D14 programmes, and currently through a COST D26 working group coordinated by Daule in Fribourg.
Current research is supported by EPSRC grant EO/E010490 to facilitate a collaboration with Daule to perform DFT calculations of organometallic dipoles and model compounds. The grant will enable Stephenson to perform DFT calculations in Fribourg, in a research group that is an international leader in the application of DFT to issues in nonlinear optics. Stephenson is also a co-investigator on a grant for nanoscale and molecular photonics at UEA (EPSRC EP/C007751).
