Chiral Amide Directed Assembly of a Diastereo- and Enantiopure Supramolecular Host and its Application to Enantioselective Catalysis of Neutral Substrates

Zhao, Chen; Sun, Qing‐Fu; Hart‐Cooper, William M.; DiPasquale, Antonio G.; Toste, F. Dean; Bergman, Robert G.; Raymond, Kenneth N.

doi:10.1021/ja411631v

Cited by 201 publications

(138 citation statements)

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“…1 and 2A) (33,34). Assembly 1 exhibits 12 intramolecular amide hydrogen bonds which, in analogy to structurally important peptide bonds found in polypeptides, preferentially stabilize the desired tetrahedral supramolecular structure over other conformers (35).…”

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confidence: 97%

“…Assembly 1 exhibits 12 intramolecular amide hydrogen bonds which, in analogy to structurally important peptide bonds found in polypeptides, preferentially stabilize the desired tetrahedral supramolecular structure over other conformers (35). Compound 1 and related hosts have been shown to catalyze several important chemical reactions with sizable rate accelerations (up to 10 6 ) and unusual selectivity reminiscent of enzyme catalysis (34,(36)(37)(38)(39)(40)(41). Unlike most enzymes, the reactions catalyzed by 1 are functionally and mechanistically very diverse.…”

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confidence: 99%

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Protein-like proton exchange in a synthetic host cavity

Hart‐Cooper

Sgarlata

Perrin

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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The mechanism of proton exchange in a metal-ligand enzyme active site mimic (compound 1) is described through amide hydrogendeuterium exchange kinetics. The type and ratio of cationic guest to host in solution affect the rate of isotope exchange, suggesting that the rate of exchange is driven by a host whose cavity is occupied by water. Rate constants for acid-, base-, and watermediated proton exchange vary by orders of magnitude depending on the guest, and differ by up to 200 million-fold relative to an alanine polypeptide. These results suggest that the unusual microenvironment of the cavity of 1 can dramatically alter the reactivity of associated water by magnitudes comparable to that of enzymes.W ater-mediated proton transfer in molecular cavities plays an essential role in the function of nature's remarkable metabolic machinery (1, 2). Of the broad diversity of enzymecatalyzed reactions, those involving transfer of hydrogen are ubiquitous and of high fundamental importance (3). For instance, ATP synthase employs an internal chain of water molecules to mediate proton transfer across an electrochemical gradient (4, 5). This process drives ATP synthesis, which allows organisms to broadly meet their basic energy needs. Recent studies of tunneling in enzymatic hydron transfer reactions have other far-reaching and broad implications, namely the importance of the dynamic enzyme motions in driving catalysis (6, 7).Of the methods used to study hydron transfer, kinetic studies of the mechanisms of amide hydrogen-deuterium exchange (HDX) have helped to elucidate the dynamic interactions between water and protein surfaces that are central to the unique capabilities of enzymes (8-13). Noncovalent interactions, such as electrostatic effects and hydrogen bonding, have also been shown to exert a significant influence on amide HDX rates. These properties are manifest in amide HDX rate constants that can vary by a factor of a billion for residues on the same protein (8). How these variations arise, and how such a property could be harnessed to drive enzyme-like reactivity, remain challenging questions.In a growing effort to emulate the efficacy of biological receptors and enzymes, studies of the preparative, guest-binding, and catalytic properties of synthetic assemblies have been pursued (14-21). Whereas guest encapsulation has been reported in a variety of media, association processes of organic guests are generally more thermodynamically favorable in water (22, 23). Central to these studies is the notion that the displacement of a high-energy water cluster from a receptor drives guest association, and in some cases, subsequent catalysis. However, despite the abundance of structural data documenting diverse water clusters encapsulated in various host cavities, mechanistic descriptions of the dynamic processes between water and host are rare (24-32).As part of the broader field of synthetic hosts previously mentioned, our group has developed a class of biologically inspired, anionic K 12 Ga 4 L 6 assemblies that exhibit cat...

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confidence: 97%

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confidence: 99%

Protein-like proton exchange in a synthetic host cavity

Hart‐Cooper

Sgarlata

Perrin

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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“…When the chiral amine subcomponent was displaced by the achiral amine tris(2-aminoethyl)amine, the cage retained its stereochemistry with high enantiomer excess (99%ee) (Figure 12) [71]. Raymond et al reported the diastereoselective formation of a tetrahedral cage assembled using six biscatecholates with chiral amide terminals and four Ga(III) cations without involving any cationic species [72]. The chiral cage possessed greater stability toward air oxidation and low pH compared to the corresponding tetrahedral cage without chiral amide terminals.…”

Section: Dynamic Production and Inversion Of Supramolecular Chiralitymentioning

confidence: 99%

Supramolecular Chirality in Dynamic Coordination Chemistry

Miyake

2014

Symmetry

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Labile metal complexes have a useful coordination bond; which is weaker than a covalent C-C bond and is reversibly and dynamically formed and dissociated. Such labile metal complexes also can be used to construct chiral shapes and offer dynamic conversion of chiral molecular shapes in response to external stimuli. This review provides recent examples of chirality induction and describes the dynamic conversion systems produced by chiral metal complexes including labile metal centers, most of which respond to external stimuli by exhibiting sophisticated conversion phenomena.

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“…At the present stage, various types of luminescent lanthanide complexes have been reported [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25]. Luminescent lanthanide coordination polymers as the thermostable luminescent materials have recently been studied.…”

Section: Introductionmentioning

confidence: 96%

Thermostable Nano Luminophores Composed of Europium Ions and Organic Ligands

Onodera

Nakajima

Nakanishi

et al. 2015

e-J. Surf. Sci. Nanotech.

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The luminescent nanoparticles with Eu(III) ions are reported. Standard nanoparticles are prepared by the reaction of europium chloride with dpp (diphenylphospinic acid) joint ligands. The size-controlled nanoparticles are synthesized by the reaction of Eu(hfa)3(H2O)2 (hfa: hexafluoroacetylacetonate) with bidentate dpbp ligands (dpbp: 4,4'-bis(diphenylphosphoryl)biphenyl) and monodentate ligands (TPPO: triphenylphosphine oxide). Their particle sizes were characterized using TEM and dynamic light scattering (DLS) measurements. Their luminescence properties were estimated by the emission spectra and lifetimes.

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Chiral Amide Directed Assembly of a Diastereo- and Enantiopure Supramolecular Host and its Application to Enantioselective Catalysis of Neutral Substrates

Cited by 201 publications

References 34 publications

Protein-like proton exchange in a synthetic host cavity

Protein-like proton exchange in a synthetic host cavity

Supramolecular Chirality in Dynamic Coordination Chemistry

Thermostable Nano Luminophores Composed of Europium Ions and Organic Ligands

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