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Molecular biomimetics is an emerging multidisciplinary science in which nature's molecular tools are combined with modem synthetic techniques in order to develop novel hybrid materials and/or to provide economically efficient, environmentally benign routes to the synthesis of compounds and polymers. The research reported here describes our recent progress in biosilicon chemistry through the use of both biocatalysts (i.e. enzymes) and novel biomimetic polymeric materials. For the first time, molecular imprinted polymers (MIPs) have been utilized for catalytic and recognition/separation purposes with respect to organosilicon substrates. Recent collaborative work between Dow Coming and the Open University led to the first unambiguous example of biocatalysis at silicon during the cleavage and formation of siloxane bonds. In particular, the active site of trypsin, a proteolytic enzyme, was found to selectively catalyze the in vitro condensation of silanols.

The aims of this work were two-fold - to enhance the 'latent functionality' of a silicon centre by expanding the range of functionalisation reactions available to such compounds, and to develop novel silicon-tethered transformations in order to increase the utility of this attractive synthetic strategy. 1. Aryle Silane Oxidation. Building upon the earlier work of Tamao and co-workers, we have developed a mild, functional group-tolerant oxidation of arylsilanes, allowing a wide range of phenols to be readily accessed. One key insight uncovered during this work was the observation that this oxidation could be acheived with sub-stoichiometric quantities of a fluoride promoter, thus allowing several TBS-protected substrates to be oxidised without any concomitant loss of the protecting group. 2. Silicon-Tethering Methodology. In order to utilise our recently acquired expertise in the field of alkoxy arylsilane synthesis, we sought to develop a novel silicon-tethered iron-catalysed biaryl coupling. Unfortunately, despite our considerable efforts, this methodology was found to suffer from reproducibility issues, and thus our attentions subsequently turned to silicon-tethered palladium- and platinum-catalysed processes. These investigations proved to be more fruitful, with the palladium-catalysed methodology affording a small range of silicon-tethered products. Finally, a novel platinum-catalysed hydro-silylation/electrocyclisation cascade was also developed, allowing a substituted arene to be accessed from a dienyne precursor.