Artificial metalloenzymes: (strept)avidin as host for enantioselective hydrogenation by achiral biotinylated rhodium-diphosphine complexes.
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). The association constant between a prototypical cationic biotinylated rhodium-diphosphine catalyst precursor and the host proteins was determined at neutral pH: log K(a) = 7.7 for avidin (pI = 10.4) and log K(a) = 7.1 for streptavidin (pI = 6.4). It is shown that the optimal operating conditions for the enantioselective reduction are 5 bar at 30 degrees C with a 1% catalyst loading.
Skander
Myriem
M
Institute of Chemistry, University of Neuchâtel, Avenue Bellevaux 51, CP2, CH-2007 Neuchâtel, Switzerland.
Humbert
Nicolas
N
Collot
Jérôme
J
Gradinaru
Julieta
J
Klein
Gérard
G
Loosli
Andreas
A
Sauser
Jérôme
J
Zocchi
Andrea
A
Gilardoni
François
F
Ward
Thomas R
TR
D000179:Acrylates / Q000737:chemistry; D001360:Avidin / Q000031:analogs & derivatives* / Q000096:biosynthesis / Q000737:chemistry / Q000235:genetics; D001412:Bacillus subtilis / Q000235:genetics / Q000378:metabolism; D001710:Biotin / Q000031:analogs & derivatives / Q000737:chemistry; D002384:Catalysis; D004798:Enzymes / Q000138:chemical synthesis / Q000737:chemistry*; D006865:Hydrogenation; D007700:Kinetics; D008667:Metalloproteins / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D016297:Mutagenesis, Site-Directed; D010720:Phosphines / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D019809:Streptavidin / Q000031:analogs & derivatives* / Q000096:biosynthesis / Q000737:chemistry / Q000235:genetics
D000179:Acrylates; D004798:Enzymes; D008667:Metalloproteins; D010720:Phosphines; D001360:Avidin; D001710:Biotin; D019809:Streptavidin; D012238:Rhodium