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A supramolecular approach to combining enzymatic and transition metal catalysis

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TLDR
A variety of catalytic tandem reactions that employ esterases, lipases or alcohol dehydrogenases and gold(I) or ruthenium(II) complexes encapsulated in a Ga4L6 tetrahedral supramolecular cluster are presented and it is suggested that encapsulation of reactive complexes may provide a general strategy for carrying out classic organic reactions in the presence of biocatalysts.
Abstract
The ability of supramolecular host-guest complexes to catalyse organic reactions collaboratively with an enzyme is an important goal in the research and discovery of synthetic enzyme mimics. Herein we present a variety of catalytic tandem reactions that employ esterases, lipases or alcohol dehydrogenases and gold(I) or ruthenium(II) complexes encapsulated in a Ga(4)L(6) tetrahedral supramolecular cluster. The host-guest complexes are tolerated well by the enzymes and, in the case of the gold(I) host-guest complex, show improved reactivity relative to the free cationic guest. We propose that supramolecular encapsulation of organometallic complexes prevents their diffusion into the bulk solution, where they can bind amino-acid residues on the proteins and potentially compromise their activity. Our observations underline the advantages of the supramolecular approach and suggest that encapsulation of reactive complexes may provide a general strategy for carrying out classic organic reactions in the presence of biocatalysts.

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Journal ArticleDOI

Applications of metal–organic frameworks in heterogeneous supramolecular catalysis

TL;DR: This review summarizes the use of metal-organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions.
Journal ArticleDOI

Supramolecular catalysis. Part 2: artificial enzyme mimics

TL;DR: Artificial catalysts and biomacromolecule hybrid catalysts which constitute good models towards the development of truly competitive artificial enzymes are presented.
Journal ArticleDOI

Supramolecular self-assemblies as functional nanomaterials

TL;DR: This compilation illustrates how, based on the rules of supramolecular chemistry, the bottom-up approach to design functional objects at the nanoscale is currently producing highly sophisticated materials oriented towards a growing number of applications with high societal impact.
Journal ArticleDOI

Molecular containers in complex chemical systems

TL;DR: Examples from the literature concerning three aspects of this field: complex host-guest behaviour, adaptive transformations of molecular containers and reactivity modulation within them are discussed.
References
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Journal ArticleDOI

Functional Molecular Flasks : New Properties and Reactions within Discrete, Self-Assembled Hosts

TL;DR: This Review briefly highlights the various molecular flasks synthesized before focusing on their use as functional molecular containers--specifically for the encapsulation of guest molecules to either engender unusual reactions or unique chemical phenomena.
Journal ArticleDOI

Diels-Alder in Aqueous Molecular Hosts: Unusual Regioselectivity and Efficient Catalysis

TL;DR: It is found that an aqueous organopalladium cage induces highly unusual regioselectivity in the Diels-Alder coupling of Anthracene and phthalimide guests, promoting reaction at a terminal rather than central anthracene ring.
Journal ArticleDOI

Selective molecular recognition, C-H bond activation, and catalysis in nanoscale reaction vessels

TL;DR: In this paper, a chiral self-assembled M4L6 supramolecular tetrahedron can encapsulate a variety of cationic guests with varying degrees of stereoselectivity.
BookDOI

Enzyme Catalysis in Organic Synthesis

TL;DR: Extended applications of Enzymatic Catalytic Promiscuity and the Design of New Enzyme Catalyzed ReactionsCatalytic Antibodies Chemoenzymatic Dynamic Kinetic Resolution and Related Dynamic Asymmetric Transformations Biocatalysis in Material Science Industrial Applications of EnZymes in Emerging Areas.
Journal ArticleDOI

Acid catalysis in basic solution: a supramolecular host promotes orthoformate hydrolysis.

TL;DR: A highly charged, water-soluble, metal-ligand assembly with a hydrophobic interior cavity that thermodynamically stabilizes protonated substrates and consequently catalyzes the normally acidic hydrolysis of orthoformates in basic solution, with rate accelerations of up to 890-fold.
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