Hydrogenation and Transfer Hydrogenation in Water

Wu, Xiao‐Feng; Xiao, Jianliang

doi:10.1002/9783527656790.ch6

Cited by 16 publications

(9 citation statements)

References 336 publications

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“…As amply demonstrated by Xiao and coworkers, closely related homogenous catalysts are efficient for the asymmetric reduction of prochiral ketones and cyclic imines in water. [232][233][234] This is obviously an important feature in the context of ArMs.…”

Section: Transfer Hydrogenationmentioning

confidence: 99%

Artificial Metalloenzymes: Reaction Scope and Optimization Strategies

et al. 2017

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The incorporation of a synthetic, catalytically competent metallocofactor into a protein scaffold to generate an artificial metalloenzyme (ArM) has been explored since the late 1970's. Progress in the ensuing years was limited by the tools available for both organometallic synthesis and protein engineering. Advances in both of these areas, combined with increased appreciation of the potential benefits of combining attractive features of both homogeneous catalysis and enzymatic catalysis, led to a resurgence of interest in ArMs starting in the early 2000's. Perhaps the most intriguing of potential ArM properties is their ability to endow homogeneous catalysts with a genetic memory. Indeed, incorporating a homogeneous catalyst into a genetically encoded scaffold offers the opportunity to improve ArM performance by directed evolution. This capability could, in turn, lead to improvements in ArM efficiency similar to those obtained for natural enzymes, providing systems suitable for practical applications and greater insight into the role of second coordination sphere interactions in organometallic catalysis. Since its renaissance in the early 2000's, different aspects of artificial metalloenzymes have been extensively reviewed and highlighted. Our intent is to provide a comprehensive overview of all work in the field up to December 2016, organized according to reaction class. Because of the wide range of non-natural reactions catalyzed by ArMs, this was done using a functional-group transformation classification. The review begins with a summary of the proteins and the anchoring strategies used to date for the creation of ArMs, followed by a historical perspective. Then follows a summary of the reactions catalyzed by ArMs and a concluding critical outlook. This analysis allows for comparison of similar reactions catalyzed by ArMs constructed using different metallocofactor anchoring strategies, cofactors, protein scaffolds, and mutagenesis strategies. These data will be used to construct a searchable Web site on ArMs that will be updated regularly by the authors.

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Section: Transfer Hydrogenationmentioning

confidence: 99%

Artificial Metalloenzymes: Reaction Scope and Optimization Strategies

et al. 2017

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“…86 TH reactions in aqueous media were not reported until the mid 1980s. 87,88 Complexes such as [RuCl 2 (PPh 3 ) 3 ], [Cp*IrCl 3 ], or [(η 6 -arene)Ru [TsDPEN)Cl] (4) were shown to reduce ketones, aldehydes, or imines in water or biphasic media (water/organic) using formate salt as a hydride donor. 87,88 The use of aqueous media seemed to increase catalytic rates and allows for the use of more environmentally friendly solvents.…”

Section: Hydrogenation and Transfer Hydrogenation Reactionsmentioning

confidence: 99%

Intracellular Catalysis with Selected Metal Complexes and Metallic Nanoparticles: Advances toward the Development of Catalytic Metallodrugs

2019

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Platinum-containing drugs (e.g., cisplatin) are among the most frequently used chemotherapeutic agents. Their tremendous success has spurred research and development of other metal-based drugs, with notable achievements. Generally, the vast majority of metal-based drug candidates in clinical and developmental stages are stoichiometric agents, i.e., each metal complex reacts only once with their biological target. Additionally, many of these metal complexes are involved in side reactions, which not only reduce the effective amount of the drug but may also cause toxicity. On a separate note, transition metal complexes and nanoparticles have a well-established history of being potent catalysts for selective molecular transformations, with examples such as the Mo- and Ru-based catalysts for metathesis reactions (Nobel Prize in 2005) or palladium catalysts for C–C bond forming reactions such as Heck, Negishi, or Suzuki reactions (Nobel Prize in 2010). Also, notably, no direct biological equivalent of these transformations exists in a biological environment such as bacteria or mammalian cells. It is, therefore, only logical that recent interest has focused on developing transition-metal based catalytic systems that are capable of performing transformations inside cells, with the aim of inducing medicinally relevant cellular changes. Because unlike in stoichiometric reactions, a catalytically active compound may turn over many substrate molecules, only very small amounts of such a catalytic metallodrug are required to achieve a desired pharmacologic effect, and therefore, toxicity and side reactions are reduced. Furthermore, performing catalytic reactions in biological systems also opens the door for new methodologies to study the behavior of biomolecules in their natural state, e.g., via in situ labeling or by increasing/depleting their concentration at will. There is, of course, an art to the choice of catalysts and reactions which have to be compatible with biological conditions, namely an aqueous, oxygen-containing environment. In this review, we aim to describe new developments that bring together the far-distant worlds of transition-metal based catalysis and metal-based drugs, in what is termed “catalytic metallodrugs”. Here we will focus on transformations that have been performed on small biomolecules (such as shifting equilibria like in the NAD+/NADH or GSH/GSSG couples), on non-natural molecules such as dyes for imaging purposes, or on biomacromolecules such as proteins. Neither reactions involving release (e.g., CO) or transformation of small molecules (e.g., 1O2 production), degradation of biomolecules such as proteins, RNA or DNA nor light-induced medicinal chemistry (e.g., photodynamic therapy) are covered, even if metal complexes are centrally involved in those. In each section, we describe the (inorganic) chemistry involved, as well as selected examples of biological applications in the hope that this snapshot of a new but quickly developing field will indeed inspire novel research and unprecedented inte...

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“…In this sense, heterogeneous hydrogenation is mainly used in the production of large-scale chemical products (NH3, MeOH or cyclohexane, among others), whereas homogeneous hydrogenation is usually employed in the synthesis of fine chemical products (drugs, hormones, fragrances, etc.). Bearing in mind the fact that hydrogenation (as a metal-catalyzed reduction with H2) is one of the most studied reactions in aqueous media (since 1960-1970) [56], is not surprising to find in the literature several reports on the combination of metal-catalyzed hydrogenations in water with different biotransformations. Thus, this section covers the progress made in the combination of the aforementioned reactions in water.…”

Section: Metal-catalyzed Hydrogenations Combined With Bioreductions mentioning

confidence: 99%

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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Hydrogenation and Transfer Hydrogenation in Water

Cited by 16 publications

References 336 publications

Artificial Metalloenzymes: Reaction Scope and Optimization Strategies

Artificial Metalloenzymes: Reaction Scope and Optimization Strategies

Intracellular Catalysis with Selected Metal Complexes and Metallic Nanoparticles: Advances toward the Development of Catalytic Metallodrugs

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

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