Chemoselective Catalysis with Organosoluble Lewis Acidic Polyoxotungstates

Dupré, Nathalie; Rémy, Pauline; Micoine, Kévin; Boglio, Cécile; Thorimbert, Serge; Lacôte, Emmanuel; Hasenknopf, Bernold; Malacrìa, Max

doi:10.1002/chem.201000411

Cited by 93 publications

(55 citation statements)

References 64 publications

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“…RE cations with high coordination numbers (typically six-12) and flexible coordination geometries can also leave residual (open) coordination sites, which would act as effective Lewis acids for the activation of substrates. Several POMs containing REs have been reported to act not only as Lewis acid catalysts but also as hydrogen-bond acceptor for aldol, imino Diels−Alder reactions or the cyanosilylation of carbonyl compounds with trimethylsilyl cyanide (TMSCN) [37,41,[105][106][107][108]. …”

Section: Transition-metal-substituted Polyoxometalatesmentioning

confidence: 99%

Base Catalysis by Mono- and Polyoxometalates

Kamata

Sugahara

2017

Catalysts

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Abstract:In sharp contrast with acid-, photo-, and oxidation-catalysis by polyoxometalates, base catalysis by polyoxometalates has scarcely been investigated. The use of polyoxometalates as base catalysts have very recently received much attention and has been extensively investigated. Numerous mono-and polyoxometalate base catalyst systems effective for the chemical fixation of CO 2 , cyanosilylation of carbonyl compounds, and C-C bond forming reactions have been developed. Mono-and polyoxometalate base catalysts are classified into four main groups with respect to their structures: (a) monomeric metalates; (b) isopolyoxometalates; (c) heteropolyoxometalates; and (d) transition-metal-substituted polyoxometalates. This review article focuses on the relationship among the molecular structures, the basic properties, and the unique base catalysis of polyoxometalates on the basis of groups (a)-(d). In addition, reaction mechanisms including the specific activation of substrates and/or reagents such as the abstraction of protons, nucleophilic action toward substrates, and bifunctional action in combination with metal catalysts are comprehensively summarized.

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Section: Transition-metal-substituted Polyoxometalatesmentioning

confidence: 99%

Base Catalysis by Mono- and Polyoxometalates

Kamata

Sugahara

2017

Catalysts

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“…For instance, Zr‐containing Keggin POM (Zr1‐K2) was found to hydrolyze less than 35% of HSA after 48 h, but the degree of hydrolysis was substantially enhanced after 192 h . However, instead of dimeric 1:2 (Zr1‐K2), the monomeric 1:1 (ZrK) form of this POM was identified as the reactive species in the hydrolysis . The Zr1‐K2 to ZrK transformation has also been reported to be assisted by the protein environment and after its formation ZrK is stabilized by electrostatic and water‐mediated hydrogen bonding interactions with the protein .…”

Section: Introductionmentioning

confidence: 99%

Hydrolysis of chemically distinct sites of human serum albumin by polyoxometalate: A hybrid QM/MM (ONIOM) study

Jayasinghe‐Arachchige

Sharma

et al. 2018

J Comput Chem

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In this study, mechanisms of hydrolysis of all four chemically diverse cleavage sites of human serum albumin (HSA) by [Zr(OH)(PW11O39)]4− (ZrK) have been investigated using the hybrid two‐layer QM/MM (ONIOM) method. These reactions have been proposed to occur through the following two mechanisms: internal attack (IA) and water assisted (WA). In both mechanisms, the cleavage of the peptide bond in the Cys392‐Glu393 site of HSA is predicted to occur in the rate‐limiting step of the mechanism. With the barrier of 27.5 kcal/mol for the hydrolysis of this site, the IA mechanism is found to be energetically more favorable than the WA mechanism (barrier = 31.6 kcal/mol). The energetics for the IA mechanism are in line with the experimentally measured values for the cleavage of a wide range of dipeptides. These calculations also suggest an energetic preference (Cys392‐Glu393, Ala257‐Asp258, Lys313‐Asp314, and Arg114‐Leu115) for the hydrolysis of all four sites of HSA. © 2018 Wiley Periodicals, Inc.

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“…Traditionally, HPA-based catalysis has focused on Brønsted acid [8,9] and oxidation [10][11][12] reactions. Recently, some studies have been conducted on developing Lewis acidic HPAs that could open new options [13][14][15][16][17][18]. In addition, some HPAs containing both Brønsted and Lewis acidity [19] have shown excellent catalytic activity for the selective hydrolysis of cellulose to glucose [20] and other acid-catalyzing reactions [21].…”

Section: Introductionmentioning

confidence: 98%

Effects of Brønsted and Lewis Acidities on Catalytic Activity of Heteropolyacids in Transesterification and Esterification Reactions

Zhao¹,

Yuan²,

Wang³

et al. 2011

Chem Eng & Technol

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PW) were prepared and used as acid catalysts for transesterification and esterification reactions. These catalysts have double acidity properties, i.e., Lewis acidity and Brønsted acidity, that are suitable for the conversion of waste cooking oil into biodiesel. The highest efficiency was 59.2 % and 94.7 % corresponding to transesterification and esterification reactions by Ti 0.6 H 0.6 PW with moderate Lewis acidity. The relationship between the acidic properties and the catalytic activity is discussed in detail.

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Chemoselective Catalysis with Organosoluble Lewis Acidic Polyoxotungstates

Cited by 93 publications

References 64 publications

Base Catalysis by Mono- and Polyoxometalates

Base Catalysis by Mono- and Polyoxometalates

Hydrolysis of chemically distinct sites of human serum albumin by polyoxometalate: A hybrid QM/MM (ONIOM) study

Effects of Brønsted and Lewis Acidities on Catalytic Activity of Heteropolyacids in Transesterification and Esterification Reactions

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