Synthetic cascades are enabled by combining biocatalysts with artificial metalloenzymes

Koehler, V. and Wilson, Y. M. and Duerrenberger, M. and Ghislieri, D. and Churakova, E. and Quinto, T. and Knoerr, L. and Haeussinger, D. and Hollmann, F. and Turner, N. J. and Ward, Thomas R.. (2013) Synthetic cascades are enabled by combining biocatalysts with artificial metalloenzymes. Nature Chemistry, 5. pp. 93-99.

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Official URL: http://edoc.unibas.ch/dok/A6070740

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Enzymic catalysis and homogeneous catalysis offer complementary means to address synthetic challenges, both in chem. and in biol.  Despite its attractiveness, the implementation of concurrent cascade reactions that combine an organometallic catalyst with an enzyme has proven challenging because of the mutual inactivation of both catalysts.  To address this, we show that incorporation of a d6-piano stool complex within a host protein affords an artificial transfer hydrogenase (ATHase) that is fully compatible with and complementary to natural enzymes, thus enabling efficient concurrent tandem catalysis.  To illustrate the generality of the approach, the ATHase was combined with various NADH-, FAD- and haem-dependent enzymes, resulting in orthogonal redox cascades.  Up to three enzymes were integrated in the cascade and combined with the ATHase with a view to achieving (i) a double stereoselective amine deracemization, (ii) a horseradish peroxidase (HRP)-coupled readout of the transfer hydrogenase activity towards its genetic optimization, (iii) the formation of L-pipecolic acid from L-lysine, and (iv) regeneration of NADH to promote a monooxygenase-catalyzed oxyfunctionalization reaction
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Bioanorganische Chemie (Ward)
05 Faculty of Science > Departement Chemie > Chemie > Nuclear Magnetic Resonance (Häussinger)
UniBasel Contributors:Ward, Thomas R. R. and Quinto, Tommaso and Knörr, Livia and Köhler, Valentin and Wilson, Yvonne Martha and Dürrenberger, Marc and Häussinger, Daniel
Item Type:Article, refereed
Article Subtype:Research Article
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:03 May 2017 09:02
Deposited On:24 May 2013 08:58

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