Artificial metalloenzymes have become a vibrant area of research. They are expected to combine supreme enzymatic selectivity with the broad range of catalytic motifs provided by homogeneous catalysts. We present our results on introducing well-defined and catalytically active metal-sites selectively into an engineered host protein. Using orthogonal tRNA/aaRS pairs, UAAs are incorporated site-specific to generate catalytically active metal centres in vivo. The site selective introduction of the metal centers is confirmed by protein X-ray structure determination. The resulting artificial metalloenzymes provide reactivities, which otherwise do not exist in nature. We validate the use of these artificial metalloenzymes for e.g. catalytic asymmetric Diels-Alder cyclisation or Tsuji-Trost cross-coupling. Our initial results demonstrate that catalytically active late transition-metal centers can be engineered into host-proteins with low metal-binding affinity by this approach without post-translational chemical protein modifications.

Enriching biocatalysis with artificial metalloenzymes

247th National Meeting (2014)

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