A Highly Active Biohybrid Catalyst for Olefin Metathesis in Water: Impact of a Hydrophobic Cavity in a β-Barrel Protein

Sauer, Daniel F.; Himiyama, Tomoki; Tachikawa, Kengo; Fukumoto, Kazuhiro; Onoda, Akira; Mizohata, Eiichi; Inoue, Tsuyoshi; Bocola, Marco; Schwaneberg, Ulrich; Hayashi, Takashi; Okuda, Jun

doi:10.1021/acscatal.5b01792

Cited by 71 publications

(87 citation statements)

References 36 publications

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“…Arnold and co-workers utilized the reactivity of iron-containing metalloenzymes 75 whereas others, such as the group of Hartwig, relied on transition metal cofactors such as iridium 76,77 . Protein scaffolds vary from CYP enzymes 75,78 to myoglobins 79 and other natural metalloenzymes 80 . The assembly of such novel catalytic entities occurred via the replacement of the natural cofactor, affinity tag technology or covalent linkage 80,81 .…”

Section: Novel Chemistries and Other Trendsmentioning

confidence: 99%

“…Protein scaffolds vary from CYP enzymes 75,78 to myoglobins 79 and other natural metalloenzymes 80 . The assembly of such novel catalytic entities occurred via the replacement of the natural cofactor, affinity tag technology or covalent linkage 80,81 . The Ward group has developed novel metalloenzymes using biotin-streptavidin technology.…”

Section: Novel Chemistries and Other Trendsmentioning

confidence: 99%

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Opportunities and challenges for combining chemo- and biocatalysis

et al. 2018

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N ature has evolved highly efficient systems in the form of cascade reactions, which assemble the metabolic networks that support life (growth and survival). The basic principle of cascade reactions is also frequently used in biocatalysis, using enzymes in isolation, as well as in combination with chemocatalysts (see Fig. 1 and Box 1 for definition of terms) [1][2][3][4][5][6][7] . As there is no need for purification and isolation of intermediates, operating time, production costs and waste are reduced, and concomitantly, overall yields are improved. In addition, the problem of unstable or difficult to handle intermediates can be overcome, and reactivity as well as selectivity can be enhanced by avoiding unfavourable reaction equilibria through the cooperative effects of multiple catalysts 8 . Starting in the 1980s, the early examples of the combination of chemo-and biocatalysts were reported by the van Bekkum group, who pioneered the development of a process to make the sugar substitute d-mannitol from readily available d-glucose through the combination of a heterogeneous metal-catalysed hydrogenation and an enzyme-catalysed isomerization 9 . The first broadly applied technology for the combination of enzyme and metalcatalysts, which was the research subject of many academic groups as well as industry, emerged in the 1990s from the Williams group 10,11 and aimed to achieve higher yields than classical kinetic resolution of racemates, thus overcoming the limitation of a maximum yield of 50% in the latter case. A prominent example of work that developed this theme is the combination of lipase-catalysed kinetic resolution via acylation of secondary alcohols with Pd-or Rh-catalysed racemization via reversible transfer hydrogenation to achieve a dynamic kinetic resolution (DKR) [12][13][14] . This example was facilitated in part because lipases are active and stable in organic solvents. Later, for instance, Turner's group combined a monoamine oxidase-catalysed imine formation with a chemical reduction 15 to achieve the 100% theoretical yield through a deracemization process. In addition to the combination of metalcatalysis with enzymes, organocatalysis, electrochemistry and light-induced reaction couples have since then been studied extensively, going far beyond the scope of a DKR.The challenges to combining chemo-and biocatalysis in cascades (see Box 1 for definitions and Table 1) can be daunting, not least the requirement for the chemical step to occur in the presence of water, the preferred solvent for enzymes 3 . This Review therefore highlights recent examples of the combination of chemo-and biocatalysts in aqueous multistep syntheses, and looks at how to overcome limitations by, for example, design of appropriate reaction conditions, protein engineering and advanced reactor concepts. Furthermore, trends such as the integration of transition metalcatalysis into microorganisms and the introduction of novel chemistry into engineered enzymes are discussed, and a critical assessment of the impact of this research ...

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Section: Novel Chemistries and Other Trendsmentioning

confidence: 99%

Section: Novel Chemistries and Other Trendsmentioning

confidence: 99%

Opportunities and challenges for combining chemo- and biocatalysis

et al. 2018

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“…In this sense, the use of immobilization technology to specific support materials or the generation of hybrids systems using protein as a scaffold to conjugate with the corresponding transition metal catalysts has been a successful example to create heterogeneous artificial metalloenzymes [9][10][11][12]. In particular, the application of enzymes with high catalytic versatility could generate higher possibilities, depending on the transition metal or metal binding ligands inserted.…”

Section: Introductionmentioning

confidence: 99%

“…The catalytic capacity of the ruthenium organometallic complex in the different protein-conjugates was evaluated in the ring-closing metathesis (RCM), among the most important C-C bond forming reactions [18][19][20] of diethyldiallymalonate (1) (Scheme 1) at mild conditions. In this sense, the use of immobilization technology to specific support materials or the generation of hybrids systems using protein as a scaffold to conjugate with the corresponding transition metal catalysts has been a successful example to create heterogeneous artificial metalloenzymes [9][10][11][12]. In particular, the application of enzymes with high catalytic versatility could generate higher possibilities, depending on the transition metal or metal binding ligands inserted.…”

Section: Introductionmentioning

confidence: 99%

Design of Heterogeneous Hoveyda–Grubbs Second-Generation Catalyst–Lipase Conjugates

2016

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Heterogeneous catalysts have been synthesized by the conjugation of Hoveyda-Grubbs second-generation catalyst with a lipase. The catalytic properties of the organometallic compound in solution were firstly optimized, evaluating the activity of Ru in the ring-closing metathesis of diethyldiallymalonate at 25 • C at different solvents and in the presence of different additives. The best result was found using tetrahydrofuran as a solvent. Some additives such as phenylboronic acid or polyetheneglycol slightly improved the activity of the Ru catalyst whereas others, such as pyridine or dipeptides affected it negatively. The organometallic compound immobilized on functionalized-surface materials activated with boronic acid or epoxy groups (around 50-60 µg per mg support) and showed 50% conversion at 24 h in the ring-closing metathesis. Cross-linked enzyme aggregates (CLEA's) of the Hoveyda-Grubbs second-generation catalyst with Candida antarctica lipase (CAL-B) were prepared, although low Ru catalyst was found to be translated in low conversion. Therefore, a sol-gel preparation of the Hoveyda-Grubbs second-generation and CAL-B was performed. This catalyst exhibited good activity in the metathesis of diethyldiallymalonate in toluene and in aqueous media. Finally, a new sustainable approach was used by the conjugation lipase-Grubbs in solid phase in aqueous media. Two strategies were used: one using lipase previously covalently immobilized on an epoxy-Sepharose support (hydrophilic matrix) and then conjugated with grubbs; and in the second, the free lipase was incubated with organometallic in aqueous solution and then immobilized on epoxy-Sepharose. The different catalysts showed excellent conversion values in the ring-closing metathesis of diethyldiallymalonate in aqueous media at 25 • C.

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“…Li, for example, is experimenting with housing enzymes inside nanoparticles 14 to help them last longer. Others are synthesizing completely artificial enzymes 15 using techniques from synthetic biology. And earlier this year, an international team of researchers reported 16 using an electric field to catalyse the formation of ring-shaped carbon compounds.…”

Section: Even-handednessmentioning

confidence: 99%

The new breed of cutting-edge catalysts

Lim¹

2016

Nature

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A Highly Active Biohybrid Catalyst for Olefin Metathesis in Water: Impact of a Hydrophobic Cavity in a β-Barrel Protein

Cited by 71 publications

References 36 publications

Opportunities and challenges for combining chemo- and biocatalysis

Opportunities and challenges for combining chemo- and biocatalysis

Design of Heterogeneous Hoveyda–Grubbs Second-Generation Catalyst–Lipase Conjugates

The new breed of cutting-edge catalysts

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