A One‐Pot Cascade Reaction Combining an Encapsulated Decarboxylase with a Metathesis Catalyst for the Synthesis of Bio‐Based Antioxidants

Baraibar, Álvaro Gómez; Reichert, Dennis; Mügge, Carolin; Seger, Svenja; Gröger, Harald; Kourist, Robert

doi:10.1002/anie.201607777

Cited by 82 publications

(75 citation statements)

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“…Another approach for combinations is the enzymatic decarboxylation of cinnamic acid derivatives to styrenes, followed by a crossmetathesis reaction for the synthesis of antioxidants, as reported by Gómez Baraibar et al 62 . They encapsulated a cofactor-free carboxylase using poly(vinyl alcohol)-poly(ethyleneglycol) cryogels, which enabled full enzymatic function in organic solvents (Fig.…”

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Opportunities and challenges for combining chemo- and biocatalysis

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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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“…Several types of metathesis transformations (RCM (ring-closing metathesis) and CM (cross-metathesis), among others) have been carried out in water by: (i) introducing modifications in the catalyst structure; (ii) using co-solvents; or (iii) employing surfactants [73][74][75]. Thus, in this section, we cover the fruitful combination of two different Ru-catalyzed metathesis protocols (RCM and CM) in aqueous media with several biocatalyzed organic reactions [76][77][78][79][80]. Although none of the discussed protocols permits the synthesis of enantiopure products, they constitute very important contributions in the field of chemoenzymatic cascade processes performed in aqueous media and are worth mention in this review.…”

Section: Combination Of Metal-catalyzed Alkene Metathesis In Water Wimentioning

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“…Not only the Ru-catalyzed ring-closing metathesis (RCM) of different diallyl compounds, but also the Ru-catalyzed cross-metathesis (CM) of functionalized olefins has been productively assembled with different biotransformations [78][79][80]. Thus, the first work in this field was reported by Zhao, Hartwig and co-workers in 2014 by describing the combination of the ruthenium-catalyzed CM between 10-undecenoic acid and trans-3-hexene with the subsequent epoxidation of the in situ-generated 10-tridecenoic acid using P450 BM3 from Bacillus megaterium in a biphasic medium [78].…”

Section: Assembly Of Ru-catalyzed Cross-metathesis (Rcm) Of Functionamentioning

confidence: 99%

“…The independent findings by Meldal [89] and Sharpless [90] on the regioselective Copper(I)-catalyzed Azide-Alkyne Cycloadditions (CuAAC) permitted the discovery of a highly-reliable tool More recently, Kourist and co-workers were able to couple the enzymatic decarboxylation of different hydroxycinnamic acids with a ruthenium catalyzed self-assembly metathesis of the in situ-generated functionalized styrenes [79] (Scheme 16). Firstly, the biocatalyzed decarboxylation of several hydroxycinnamic acids promoted by the co-factor-free phenolic acid decarboxylase (bsPAD) was studied in a potassium phosphate buffer (KPi pH 6) at 30 • C (Scheme 16A).…”

Section: Combination Of Copper-catalyzed Click Chemistry Cycloadditiomentioning

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One-Pot Combination of Metal- and Bio-Catalysis in Water for the Synthesis of Chiral Molecules

2018

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During the last decade, the combination of different metal-and bio-catalyzed organic reactions in aqueous media has permitted the flourishing of a variety of one-pot asymmetric multi-catalytic reactions devoted to the construction of enantiopure and high added-value chemicals under mild reaction conditions (usually room temperature) and in the presence of air. Herein, a comprehensive account of the state-of-the-art in the development of catalytic networks by combining metallic and biological catalysts in aqueous media (the natural environment of enzymes) is presented. Among others, the combination of metal-catalyzed isomerizations, cycloadditions, hydrations, olefin metathesis, oxidations, C-C cross-coupling and hydrogenation reactions, with several biocatalyzed transformations of organic groups (enzymatic reduction, epoxidation, halogenation or ester hydrolysis), are discussed.

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“…To overcome mutual inactivation of both catalysts, Wacker oxidation was conducted in the interior of a polydimethylsiloxane (PDMS) thimble that enabled the diffusion of only the organic substrate and product into the exterior where the biotransformation takes place (Scheme 8). In another example, they developed a one-pot cascade reaction combining a co-factor free decarboxylase from Bacillus subtilis named bsPAD with a Ru metathesis catalyst to produce high-value antioxidants in good yield from bio-based precursors [68]. Encapsulation of bsPAD in an aqueous environment created by poly(vinyl alcohol)/poly(ethylene glycol) (PAV/PEG) cryogels enabled the enzyme functionalize in pure organic solvent (Scheme 9).…”

Section: Concurrent Tandem Reactions By Transition-metal Complexes Anmentioning

confidence: 99%

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

Wang

Zhao

2016

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Abstract:The application of biocatalysts in the synthesis of fine chemicals and medicinal compounds has grown significantly in recent years. Particularly, there is a growing interest in the development of one-pot tandem catalytic systems combining the reactivity of a chemical catalyst with the selectivity engendered by the active site of an enzyme. Such tandem catalytic systems can achieve levels of chemo-, regio-, and stereo-selectivities that are unattainable with a small molecule catalyst. In addition, artificial metalloenzymes widen the range of reactivities and catalyzed reactions that are potentially employable. This review highlights some of the recent examples in the past three years that combined transition metal catalysis with enzymatic catalysis. This field is still in its infancy. However, with recent advances in protein engineering, catalyst synthesis, artificial metalloenzymes and supramolecular assembly, there is great potential to develop more sophisticated tandem chemoenzymatic processes for the synthesis of structurally complex chemicals.

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A One‐Pot Cascade Reaction Combining an Encapsulated Decarboxylase with a Metathesis Catalyst for the Synthesis of Bio‐Based Antioxidants

Cited by 82 publications

References 35 publications

Opportunities and challenges for combining chemo- and biocatalysis

Opportunities and challenges for combining chemo- and biocatalysis

One-Pot Combination of Metal- and Bio-Catalysis in Water for the Synthesis of Chiral Molecules

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

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