An enantioselective artificial Suzukiase based on the biotin–streptavidin technology

Chatterjee, Anamitra; Mallin, Hendrik; Klehr, Juliane; Vallapurackal, Jaicy; Finke, Aaron D.; Vera, Laura; Marsh, M.; Ward, Thomas R.

doi:10.1039/c5sc03116h

Cited by 94 publications

(66 citation statements)

References 44 publications

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“…This feature offers the possibility to anchor abiotic cofactors within a protein environment to create artificial metalloenzymes. ArMs based on the biotin‐Sav technology have been developed to catalyze a wide variety of water compatible reactions including: olefin metathesis, Suzuki ‐coupling, C–H activation, or transfer hydrogenation, etc …”

Section: Introductionmentioning

confidence: 99%

Photo‐Driven Hydrogen Evolution by an Artificial Hydrogenase Utilizing the Biotin‐Streptavidin Technology

Keller

Probst

Heinisch

et al. 2018

Helvetica Chimica Acta

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Photocatalytic hydrogen evolution by an artificial hydrogenase based on the biotin‐streptavidin technology is reported. A biotinylated cobalt pentapyridyl‐based hydrogen evolution catalyst (HEC) was incorporated into different mutants of streptavidin. Catalysis with [Ru(bpy)3]Cl2 as a photosensitizer (PS) and ascorbate as sacrificial electron donor (SED) at different pH values highlighted the impact of close lying amino acids that may act as a proton relay under the reaction conditions (Asp, Arg, Lys). In the presence of a close‐lying lysine residue, both, the rates were improved, and the reaction was initiated much faster. The X‐ray crystal structure of the artificial hydrogenase reveals a distance of 8.8 Å between the closest lying Co‐moieties. We thus suggest that the hydrogen evolution mechanism proceeds via a single Co centre. Our findings highlight that streptavidin is a versatile host protein for the assembly of artificial hydrogenases and their activity can be fine‐tuned via mutagenesis.

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Section: Introductionmentioning

confidence: 99%

Photo‐Driven Hydrogen Evolution by an Artificial Hydrogenase Utilizing the Biotin‐Streptavidin Technology

Keller

Probst

Heinisch

et al. 2018

Helvetica Chimica Acta

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“…In highly enantioselective Suzuki-Miyaura couplings, palladium complexes of significantly sterically hindered ligands are usually used [16,18]. Accurate computer calculations of such large complexes need an extremely large computational cost.…”

Section: Methodsmentioning

confidence: 99%

“…Among all cross-coupling reactions, only the asymmetric Heck coupling (and its several modifications, e.g., the Fujiwara-Moritani reaction and oxidative boron Heck-type reactions) is well developed [13][14][15]. At the same time, the enantioselective approach to other coupling reactions still remains challenging [16][17][18]. Without clear understanding of the mechanism of chirality transfer from the chiral catalyst to the product, a rational design of an efficient catalyst, tailored for a given enantioselective coupling reaction, remains not possible and consequent testing of a large quantity of similar ligands will be a costly alternative [18,19].…”

Section: Introductionmentioning

confidence: 99%

A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling Reaction

Jasiński

Demchuk

Babyuk

2017

Journal of Chemistry

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The DFT calculations of the simplified model of the asymmetric Suzuki-Miyaura coupling reaction were performed at the M062x/LANL2DZ theory level at first. It was found that enantioselective reactions mediated by the palladium complexes of chiral C,P-ligands follow a four-stage mechanism similar to that proposed previously as one of the most credible mechanisms. It should be underlined that the presence of substituents in the substrates and the chiral ligand at ortho positions determines the energies of possible diastereoisomeric transition states and intermediates in initial reaction steps. This suggests that, in practice, a sharp selection of theoretically possible paths of chirality transfer from the catalyst to the product should have a place and, therefore, the absolute configuration of the formed atropisomeric product is defined and can be predicted.

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“…Durch Kombination dieser Mutation mit Mutationen an Position S112 oder N118 wurde mit S112Y‐K121E eine Mutante erhalten, die eine quantitative Ausbeute mit 90 % ee lieferte. Dieser Hybridkatalysator wirkt bei vielen Aryliodiden effizient und ergibt hohe Ausbeuten …”

Section: Supramolekulare Kupplungunclassified

Genetische Optimierung von Metalloenzymen: Weiterentwicklung von Enzymen für nichtnatürliche Reaktionen

Hyster

Ward²

2016

Angewandte Chemie

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In der letzten Dekade fanden künstliche Metalloenzyme einige Aufmerksamkeit als eine mögliche Lösung für ungeklärte Probleme der organischen Synthesechemie. Während gängige Übergangsmetallkatalysatoren meist nur die erste Koordinationssphäre nutzen, um Reaktivität und Selektivität zu kontrollieren, können künstliche Metalloenzyme sowohl die erste als auch die zweite Koordinationssphäre modulieren. Dieser Unterschied manifestiert sich in den teilweise einzigartigen Reaktivitätsprofilen künstlicher Metalloenzyme. Dieser Aufsatz fasst die Versuche zusammen, die zweite Koordinationssphäre künstlicher Metalloenzyme durch genetische Modifizierungen der Proteinsequenz anzupassen. Es werden erfolgreiche Versuche und kreative Wege zur Überwindung aufgetretener Schwierigkeiten hervorgehoben.

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An enantioselective artificial Suzukiase based on the biotin–streptavidin technology

Cited by 94 publications

References 44 publications

Photo‐Driven Hydrogen Evolution by an Artificial Hydrogenase Utilizing the Biotin‐Streptavidin Technology

Photo‐Driven Hydrogen Evolution by an Artificial Hydrogenase Utilizing the Biotin‐Streptavidin Technology

A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling Reaction

Genetische Optimierung von Metalloenzymen: Weiterentwicklung von Enzymen für nichtnatürliche Reaktionen

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