Department of Chemistry

Nitschke Group

Synthetic Methodology

Synthetic Methodology

We're also interested in using self-assembly in new ways to answer questions in the domain of organic synthesis. In "Synthetic selectivity through avoidance of valence frustration" Proc. Natl. Acad. Sci. USA, 2006, 103, 17655-17660, we found a new way to solve an old synthetic problem-how to get each of two identical functional groups of a symmetrical molecule (2,6-diformylpyridine, below) to react with a different substrate, without obtaining statistical mixtures of products. The selectivity derives from the fact that the dicopper product structure shown below is the smallest one that can be generated from this collection of building blocks in which all copper(I) ions are tetracoordinate and all ligand nitrogen atoms are bound to copper.

It is possible to "turn off" the dynamic exchange processes that underlie the high selectivity of this synthesis, once they have done their job in allowing "incorrect" structures to rearrange and "anneal" into correct ones: treatment with borohydride converted the dynamic imine bonds into reduced, stabilised secondary amines. We are currently investigating ways to generalise this method, rendering it applicable to a wider range of substrates.

synthetic methodology

We are also interested in metal-catalysed organic transformations, although our studies in this area are preliminary.