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Hybrid Catalysts for Asymmetric Catalysis

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Bioorganic Chemistry".

Deadline for manuscript submissions: closed (15 June 2020) | Viewed by 11551

Special Issue Editor


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Guest Editor
Department of Pharmaceutical Science, University of Milan, Via Golgi 19, 20133 Milan, Italy
Interests: organometallic chemistry; asymmetric catalysis; hybrid catalysts; transition metal-based anticancer drugs
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Special Issue Information

Dear Colleagues,

Biological macromolecules, in general, possess the ability to selectively discriminate substrates and represent a target for specific active molecules. Otherwise, there are many chemical transformations catalyzed by transition metals, which have not been observed to occur enzymatically. Starting from these premises, a hybrid catalyst may combine some of the most attractive features of homogeneous and enzymatic catalysts. The development of a hybrid catalyst results, in fact, from the combination of a biomolecular scaffold (e.g., proteins, DNA, or peptides) with an active catalytic moiety. The three key parameters in the design of an artificial metalloenzyme can be summarized by the choice of transition metal catalyst, principally guided by the desired catalytic activity; by the choice of biomolecular scaffold, through two different strategies, de novo design or the modification of an existing natural enzyme or protein; and, finally, by the attachment mode between the transition metal catalyst and the scaffold.

This Special Issue covers all the indicated aspects of the design of a hybrid catalyst and its applications in asymmetric catalytic reactions, both as original research articles and as reviews.

Dr. Isabella Rimoldi
Guest Editor

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Keywords

  • Asymmetric catalysis
  • Hybrid catalysts
  • Artificial metallo-enzymes
  • Transition metal complexes
  • Biological scaffold interactions

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Published Papers (2 papers)

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Research

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11 pages, 1032 KiB  
Article
Streptavidin-Hosted Organocatalytic Aldol Addition
by Nicolò Santi, Louis C. Morrill and Louis Y. P. Luk
Molecules 2020, 25(10), 2457; https://doi.org/10.3390/molecules25102457 - 25 May 2020
Cited by 10 | Viewed by 4859
Abstract
In this report, the streptavidin-biotin technology was applied to enable organocatalytic aldol addition. By attaching pyrrolidine to the valeric motif of biotin and introducing it to streptavidin (Sav), a protein-based organocatalytic system was created, and the aldol addition of acetone with p-nitrobenzaldehyde [...] Read more.
In this report, the streptavidin-biotin technology was applied to enable organocatalytic aldol addition. By attaching pyrrolidine to the valeric motif of biotin and introducing it to streptavidin (Sav), a protein-based organocatalytic system was created, and the aldol addition of acetone with p-nitrobenzaldehyde was tested. The conversion of substrate to product can be as high as 93%. Although the observed enantioselectivity was only moderate (33:67 er), further protein engineering efforts can be included to improve the selectivity. These results have proven the concept that Sav can be used to host stereoselective aldol addition. Full article
(This article belongs to the Special Issue Hybrid Catalysts for Asymmetric Catalysis)
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Review

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42 pages, 13978 KiB  
Review
Artificial Metalloenzymes: From Selective Chemical Transformations to Biochemical Applications
by Tomoki Himiyama and Yasunori Okamoto
Molecules 2020, 25(13), 2989; https://doi.org/10.3390/molecules25132989 - 30 Jun 2020
Cited by 13 | Viewed by 6293
Abstract
Artificial metalloenzymes (ArMs) comprise a synthetic metal complex in a protein scaffold. ArMs display performances combining those of both homogeneous catalysts and biocatalysts. Specifically, ArMs selectively catalyze non-natural reactions and reactions inspired by nature in water under mild conditions. In the past few [...] Read more.
Artificial metalloenzymes (ArMs) comprise a synthetic metal complex in a protein scaffold. ArMs display performances combining those of both homogeneous catalysts and biocatalysts. Specifically, ArMs selectively catalyze non-natural reactions and reactions inspired by nature in water under mild conditions. In the past few years, the construction of ArMs that possess a genetically incorporated unnatural amino acid and the directed evolution of ArMs have become of great interest in the field. Additionally, biochemical applications of ArMs have steadily increased, owing to the fact that compartmentalization within a protein scaffold allows the synthetic metal complex to remain functional in a sea of inactivating biomolecules. In this review, we present updates on: (1) the newly reported ArMs, according to their type of reaction, and (2) the unique biochemical applications of ArMs, including chemoenzymatic cascades and intracellular/in vivo catalysis. We believe that ArMs have great potential as catalysts for organic synthesis and as chemical biology tools for pharmaceutical applications. Full article
(This article belongs to the Special Issue Hybrid Catalysts for Asymmetric Catalysis)
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