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Molecular machines for catalysis

Abstract

The past few decades have seen tremendous progress in the synthesis and operation of molecular systems capable of controlled mechanical movement. Here, we review the use of molecular machines as catalysts for controlling chemical reactions. We highlight the various catalyst designs with a focus on how mechanical motion is used to control catalysis with varying degrees of success. This Review discusses the current challenges of designing effective catalysts, the scope and limitations of various systems and the future potential and aims for the field. Although it is difficult to predict which concepts will become most important, as much of the work is at the proof-of-concept level, it seems clear that molecular machines have the potential to substantially impact the field of catalysis.

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Figure 1: Two-state mechanically switchable catalysts.
Figure 2: Catalyst based on a four-state mechanical switch.
Figure 3: Chiral catalysts and ligands based on light switchable, overcrowded alkene motors.
Figure 4: Allosteric catalysis.
Figure 5: Catalysis by molecular tweezers.
Figure 6: Unifunctional rotaxane-based catalysts.
Figure 7: Bistate bifunctional rotaxane-based catalysts.
Figure 8: Processive catalysis.
Figure 9: Molecular transporter systems and a stereodivergent molecular machine.

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Acknowledgements

The authors are grateful to the Engineering and Physical Sciences Research Council (EPSRC) Centre for Doctoral Training in Synthesis for Biology and Medicine (EP/L015838/1) for studentships, generously supported by AstraZeneca, Diamond Light Source, Defence Science and Technology Laboratory, Evotec, GlaxoSmithKline, Janssen, Novartis, Pfizer, Syngenta, Takeda, UCB and Vertex.

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Contributions

L.v.D., M.J.T., R.S., O.A.S. and H.A.P.B. contributed equally to the preparation of the article and are listed in reverse alphabetical order. S.P.F. directed the project.

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Correspondence to Stephen P. Fletcher.

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Glossary

Molecular machines

Systems in which a stimulus triggers the controlled motion of one molecular or submolecular component relative to another and potentially results in a net task (or work) being done.

Molecular switches

Molecules that can be reversibly shifted between two or more stable states. An important distinction between molecular switches and motors is that when switches return to their original state, any mechanical work is undone.

Allosteric regulation

The regulation of the structure and activity of a catalyst by the binding of a ligand at a site topologically distinct from the catalytically active site.

Chemoselectivity

The preferential reaction of one functional group over another in a chemical reaction.

Stereoselectivity

The preferential formation of one stereoisomer over another in a chemical reaction. If the stereoisomers are enantiomers, enantioselectivity applies (quantified by the enantiomeric excess, e.e., or enantiomeric ratio, e.r.); if they are diastereomers, diastereoselectivity applies (quantified by the diastereomeric ratio, d.r.).

Mechanical bonding

This results from an interlocked molecular architecture. Mechanically interlocked molecules cannot be separated without breaking covalent bonds.

Distributive catalysis

The most common mode of operation for homogeneous and heterogeneous catalysis in which conversion occurs at a single site before dissociation of the catalyst.

Processive catalysis

A process in which a catalyst remains attached to the substrate and performs multiple rounds of catalysis before dissociation.

Stereodivergent synthesis

A synthetic approach capable of selectively producing all the possible stereoisomers of a molecule.

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van Dijk, L., Tilby, M., Szpera, R. et al. Molecular machines for catalysis. Nat Rev Chem 2, 0117 (2018). https://doi.org/10.1038/s41570-018-0117

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