Journal ArticleDOI
Synthetic cascades are enabled by combining biocatalysts with artificial metalloenzymes
Valentin Köhler,Yvonne M. Wilson,Marc Dürrenberger,Diego Ghislieri,Ekaterina Churakova,Tommaso Quinto,Livia Knörr,Daniel Häussinger,Frank Hollmann,Nicholas J. Turner,Thomas R. Ward +10 more
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TLDR
An artificial transfer hydrogenase, based on the incorporation of a biotinylated iridium-piano-stool complex in streptavidin, is shown to be fully compatible with a range of biocatalysts and enables the concurrent interplay with oxidative enzymes.Abstract:
Enzymatic catalysis and homogeneous catalysis offer complementary means to address synthetic challenges, both in chemistry and in biology. Despite its attractiveness, the implementation of concurrent cascade reactions that combine an organometallic catalyst with an enzyme has proven challenging because of the mutual inactivation of both catalysts. To address this, we show that incorporation of a d(6)-piano stool complex within a host protein affords an artificial transfer hydrogenase (ATHase) that is fully compatible with and complementary to natural enzymes, thus enabling efficient concurrent tandem catalysis. To illustrate the generality of the approach, the ATHase was combined with various NADH-, FAD- and haem-dependent enzymes, resulting in orthogonal redox cascades. Up to three enzymes were integrated in the cascade and combined with the ATHase with a view to achieving (i) a double stereoselective amine deracemization, (ii) a horseradish peroxidase-coupled readout of the transfer hydrogenase activity towards its genetic optimization, (iii) the formation of L-pipecolic acid from L-lysine and (iv) regeneration of NADH to promote a monooxygenase-catalysed oxyfunctionalization reaction.read more
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Metals and Metal Complexes in Cooperative Catalysis with Enzymes within Organic‐Synthetic One‐Pot Processes
Journal ArticleDOI
In Vitro and In Vivo One-Pot Deracemization of Chiral Amines by Reaction Pathway Control of Enantiocomplementary ω-Transaminases
TL;DR: The in vitro cascade reaction could be successfully implemented in a livable quantity and afforded one-pot deracemization of various chiral amines with >99% eeS and 85–99% reaction yields of the resulting S-amine products.
Journal ArticleDOI
Enhanced Photocatalytic Hydrogen Production by Hybrid Streptavidin-Diiron Catalysts
Anindya Roy,Anindya Roy,Michael D. Vaughn,John Tomlin,Garrett Booher,Gerdenis Kodis,Chad R. Simmons,James P. Allen,Giovanna Ghirlanda +8 more
TL;DR: Transient absorption spectroscopy data suggest a mechanism for the observed increase in activity underpinned by an observed longer lifetime for the catalytic species Fe(I)Fe(0) when incorporated within streptavidin compared to the biotinylated catalyst in solution.
Journal ArticleDOI
Unlocking the therapeutic potential of artificial metalloenzymes.
Katsunori Tanaka,Kenward Vong +1 more
TL;DR: This review aims to highlight some important studies that have begun to take the next step within this field; namely the development of ArM-centered drug therapies or biotechnological tools.
Journal ArticleDOI
Solvent-promoted highly selective dehydrogenation of tetrahydroisoquinolines without catalyst and hydrogen acceptor
TL;DR: In this article, an unusual solvent DMF-promoted dehydrogenation of 1-substituted 1,2,3,4-tetrahydroisoquinolines to synthesize cyclic imines is described.
References
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