What? The Sharpless Asymmetric Aminohydroxylation (AA) involves the selective addition of an amino and a hydroxyl group across a double bond.

How? The AA uses an osmium catalyst based on chiral cinchona alkaloid derived ligands, with which the alkene substrate interacts. We have carried out theoretical and experimental investigations into the factors affecting this interaction, leading to general substrate design principles for controlling the outcome of the reaction.

Why? The amino alcohol functional group array is present in many natural products. The ability to selectively access one regioisomer over the other will greatly increase its scope in natural product synthesis, including the synthesis of amino sugars and amino acids.

Carbenes can be found in many areas of chemistry, from organic reactions to the interstellar medium. Despite their ubiquity, very little was known about their reaction dynamics and electronic structure until the mid-nineties when our research in this area began. Our investigations of carbenes have taken several forms. In the lab we have used several forms of laser spectroscopy, and out of the lab we have performed both ab initio calculations and simulations of spectra using experimentally obtained constants. The key results of our work are knowledge of the photochemical fates of a series of triatomic carbenes, and a better understanding of the electronic structure that governs these fates.

The rates and mechanism of reduction of platinum(IV) anticancer complexes by endogenous biomolecules in vitro have been extensively investigated. However, no reliable spectroscopic method for observing the reduction of platinum(IV) complexes in biological systems has been reported. Current techniques do not allow for facile in situ determination of the average or component oxidation states of a system. Here we describe the use of techniques to provide information about the relative proportions of platinum(II) and platinum(IV) complexes in biological systems. Using XANES, the intracellular reduction of platinum(IV) complexes in cancer cells has been observed directly, and the proportion of reduction after 2 h was found to correlate with their reduction potentials. The localisation of a number of platinum(IV) complexes has been investigated using micro-SRIXE imaging of ovarian cancer cells, revealing that cellular distribution of the complexes is similar to that of cisplatin. The cytotoxicity and lipophilicity of platinum(IV) complexes with a range of reduction potentials have been determined to elucidate their importance.