Chemical optimization of artificial metalloenzymes based on the biotin-avidin technology: (S)-selective and solvent-tolerant hydrogenation catalysts via the introduction of chiral amino acid spacers.
نویسندگان
چکیده
Incorporation of biotinylated-[rhodium(diphosphine)]+ complexes, with enantiopure amino acid spacers, in streptavidin affords solvent-tolerant and selective artificial metalloenzymes: up to 91% ee (S) in the hydrogenation of N-protected dehydroamino acids.
منابع مشابه
Second Generation Artificial Hydrogenases Based on the Biotin-Avidin Technology: Improving Activity, Stability and Selectivity by Introduction of Enantiopure Amino Acid Spacers
We report on our efforts to create efficient artificial metalloenzymes for the enantioselective hydrogenation of N-protected dehydroamino acids using either avidin or streptavidin as host proteins. Introduction of chiral amino acid spacers – phenylalanine or proline – between the biotin anchor and the flexible aminodiphosphine moiety 1, combined with saturation mutagenesis at position S112X of ...
متن کاملArtificial metalloenzymes based on biotin-avidin technology for the enantioselective reduction of ketones by transfer hydrogenation.
Most physiological and biotechnological processes rely on molecular recognition between chiral (handed) molecules. Manmade homogeneous catalysts and enzymes offer complementary means for producing enantiopure (single-handed) compounds. As the subtle details that govern chiral discrimination are difficult to predict, improving the performance of such catalysts often relies on trial-and-error pro...
متن کاملArtificial metalloenzymes for enantioselective catalysis based on the noncovalent incorporation of organometallic moieties in a host protein.
Enzymatic and homogeneous catalysis offer complementary means to produce enantiopure products. Incorporation of achiral, biotinylated aminodiphosphine-rhodium complexes in (strept)avidin affords enantioselective hydrogenation catalysts. A combined chemogenetic procedure allows the optimization of the activity and the selectivity of such artificial metalloenzymes: the reduction of acetamidoacryl...
متن کاملArtificial metalloenzymes for olefin metathesis based on the biotin-(strept)avidin technology.
Incorporation of a biotinylated Hoveyda-Grubbs catalyst within (strept)avidin affords artificial metalloenzymes for the ring-closing metathesis of N-tosyl diallylamine in aqueous solution. Optimization of the performance can be achieved either by chemical or genetic means.
متن کاملMetal-Conjugated Affinity Labels: A New Concept to Create Enantioselective Artificial Metalloenzymes
Incorporation of artificial metal centers into proteins and peptides has emerged as an important tool in chemical and biological research. Current applications include pharmaceuticals, probes for molecular imaging and contrast agents, tools for biophysical studies targeting metalloprotein functions, metal-directed protein assembly, electrochemical biosensors, and altered electrochemical potenti...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- Chemical communications
دوره 38 شماره
صفحات -
تاریخ انتشار 2005