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Artificial transfer hydrogenases based on the biotin-(strept)avidin technology : fine tuning the selectivity by saturation mutagenesis of the host protein

Letondor, Christophe and Pordea, Anca and Humbert, Nicolas and Ivanova, Anita and Mazurek, Sylwester and Novic, Marjana and Ward, Thomas R.. (2006) Artificial transfer hydrogenases based on the biotin-(strept)avidin technology : fine tuning the selectivity by saturation mutagenesis of the host protein. Journal of the American Chemical Society, 128 (25). pp. 8320-8328.

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Official URL: http://edoc.unibas.ch/dok/A5254458

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Abstract

Incorporation of biotinylated racemic three-legged d6-piano stool complexes in streptavidin yields enantioselective transfer hydrogenation artificial metalloenzymes for the reduction of ketones. Having identified the most promising organometallic catalyst precursors in the presence of wild-type streptavidin, fine-tuning of the selectivity is achieved by saturation mutagenesis at position S112. This choice for the genetic optimization site is suggested by docking studies which reveal that this position lies closest to the biotinylated metal upon incorporation into streptavidin. For aromatic ketones, the reaction proceeds smoothly to afford the corresponding enantioenriched alcohols in up to 97% ee (R) or 70% (S). On the basis of these results, we suggest that the enantioselection is mostly dictated by CH/π interactions between the substrate and the η6-bound arene. However, these enantiodiscriminating interactions can be outweighed in the presence of cationic residues at position S112 to afford the opposite enantiomers of the product.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Bioanorganische Chemie (Ward)
UniBasel Contributors:Ward, Thomas R. R.
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0002-7863
e-ISSN:1520-5126
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:24 Apr 2017 13:06
Deposited On:22 Mar 2012 14:07

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