Université de Neuchâtel

Artificial Metalloenzymes: (Strept)avidin as Host for Enantioselective Hydrogenation by Achiral Biotinylated Rhodium−Diphosphine Complexes

Skander, Myriem ; Humbert, Nicolas ; Collot, Jérôme ; Gradinaru, Julieta ; Klein, Gérard ; Loosli, Andreas ; Sauser, Jérôme ; Zocchi, Andrea ; Gilardoni, François ; Ward, Thomas R.

In: Journal of the American Chemical Society (JACS), 2004, vol. 126, no. 44, p. 14411–14418

We report on the generation of artificial metalloenzymes based on the noncovalent incorporation of biotinylated rhodium−diphosphine complexes in (strept)avidin as host proteins. A chemogenetic optimization procedure allows one to optimize the enantioselectivity for the reduction of acetamidoacrylic acid (up to 96% ee (R) in streptavidin S112G and up to 80% ee (S) in WT avidin)....

Université de Neuchâtel

Artificial Metalloenzymes for Enantioselective Catalysis Based on Biotin−Avidin

Collot, Jérôme ; Gradinaru, Julieta ; Humbert, Nicolas ; Skander, Myriem ; Zocchi, Andrea ; Ward, Thomas R.

In: Journal of the American Chemical Society (JACS), 2003, vol. 125, no. 30, p. 9030-9031

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...

Université de Neuchâtel

Artificial metalloenzymes for enantioselective catalysis : the phenomenon of protein accelerated catalysis

Collot, Jérôme ; Humbert, Nicolas ; Skander, Myriem ; Klein, Gérard ; Ward, Thomas R.

In: Journal of Organometallic Chemistry, 2005, vol. 689, p. 4868-4871

We report on the phenomenon of protein-accelerated catalysis in the field of artificial metalloenzymes based on the non-covalent incorporation of biotinylated rhodium–diphosphine complexes in (strept)avidin as host proteins. By incrementally varying the [Rh(COD)(Biot-1)]+ vs. (strept)avidin ratio, we show that the enantiomeric excess of the produced acetamidoalanine decreases slowly....

Université de Neuchâtel

Métalloenzymes artificielles pour l’hydrogénation énantiosélective basées sur la technologie biotine-avidine

Collot, Jérôme ; Ward, Thomas (Dir.)

Thèse de doctorat : Université de Neuchâtel : 2004 ; 1753.

Dans le domaine de la catalyse énantiosélective, la seconde sphère de coordination (solvant, contre-ions, etc…) influence fortement les propriétés du catalyseur. En exploitant les faibles intéractions qui régissent la seconde sphère de coordination, nous avons incorporé un catalyseur précurseur achiral dans une protéine, offrant ainsi un environnement chiral bien défini autour du...