Supramolecular Strategies for Controlling Reactivity within Confined Nanospaces

Nanospaces are ubiquitous in the realm of biological systems and are of significant interest among supramolecular chemists. Understanding chemical behavior within nanospaces offers new perspectives on biological phenomena in nature and opens the way to highly unusual and selective forms of catalysis...

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Vydáno v:Angewandte Chemie International Edition Ročník 59; číslo 33; s. 13712 - 13721
Hlavní autoři: Wang, Kaiya, Jordan, Jacobs H., Hu, Xiao‐Yu, Wang, Leyong
Médium: Journal Article
Jazyk:angličtina
Vydáno: Germany Wiley Subscription Services, Inc 10.08.2020
Vydání:International ed. in English
Témata:
Acceleration
active-site incorporation
Biological activity
Bonding strength
Catalysis
Catalytic Domain
Chemical behavior
Chemical reactions
Chemists
Hydrogen bonding
Hydrophobicity
Models, Molecular
Molecular structure
nanospaces
Nanotechnology
reactivity control
Selectivity
Substrate specificity
Substrates
supramolecular strategies
transition-state stabilization
active-site incorporation
reactivity control
supramolecular strategies
transition-state stabilization
nanospaces
ISSN:1433-7851, 1521-3773, 1521-3773
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Popis
Shrnutí:Nanospaces are ubiquitous in the realm of biological systems and are of significant interest among supramolecular chemists. Understanding chemical behavior within nanospaces offers new perspectives on biological phenomena in nature and opens the way to highly unusual and selective forms of catalysis. Supramolecular chemistry exploits weak, yet effective, intermolecular interactions such as hydrogen bonding, metal‐ligand coordination, and the hydrophobic effect to assemble nano‐sized molecular architectures, providing reactions with remarkable rate acceleration, substrate specificity, and product selectivity. In this minireview, the focus is on the strategies that supramolecular chemists use to emulate the efficiency of biological processes, and elucidating how chemical reactivity is efficiently controlled within well‐defined nanospaces. Approaches such as orientation and proximity of substrate, transition‐state stabilization, and active‐site incorporation will be discussed. Three supramolecular strategies to control reactivity within nanospaces are presented. These nano‐environments may: 1) restrict substrate conformation and enforce preorganization; 2) allow for stabilization of transition state; or 3) incorporate with the requisite active site or an additional catalyst. The synergistic effects may result in rather large rate accelerations and high selectivity.
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202000045