A cyclodextrin dimer as a supramolecular reaction platform for aqueous organometallic catalysis

Blaszkiewicz, Claire; Bricout, H.; Léonard, Estelle; Len, Christophe; Landy, David; Cézard, Christine; Djedaïni‐Pilard, Florence; Monflier, Éric; Tilloy, S.

doi:10.1039/c3cc43647k

Cited by 28 publications

(23 citation statements)

References 43 publications

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“…Note added in proof: Several papers germane to the this Review have appeared since completion of the search. These include the application of MCV to a metal-catalyzed dehydrogenative C À N bond formation, [67] a Rh-catalyzed hydroacylation, [68] organometallic associations with cyclodextrins, [69] and coordination of pincer ligands to Pd. [70] We thank the National Institutes of Health (GM077167) for direct support of this work, Leah McEwen for extensive help with construction of the literature search, and Dr. Marshall Hayes for help with some translations.…”

Section: Literature Search Protocolmentioning

confidence: 99%

Method of Continuous Variations: Applications of Job Plots to the Study of Molecular Associations in Organometallic Chemistry

et al. 2013

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Applications of the method of continuous variations—MCV or the Method of Job—to problems of interest to organometallic chemists are described. MCV provides qualitative and quantitative insights into the stoichiometries underlying association of m molecules of A and n molecules of B to form AmBn. Applications to complex ensembles probe associations that form metal clusters and aggregates. Job plots in which reaction rates are monitored provide relative stoichiometries in rate-limiting transition structures. In a specialized variant, ligand- or solvent-dependent reaction rates are dissected into contributions in both the ground states and transition states, which affords insights into the full reaction coordinate from a single Job plot. Gaps in the literature are identified and critiqued.

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Section: Literature Search Protocolmentioning

confidence: 99%

Method of Continuous Variations: Applications of Job Plots to the Study of Molecular Associations in Organometallic Chemistry

et al. 2013

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“…Moreover, using tetrabutyl Concurrently to supramolecular systems acting as second-(and possibly first-) sphere ligands, self-assembled systems where CDs only acted as a second-sphere ligand were also developed. For example, CD dimers acted as molecular platforms capable of supramolecularly interacting with both catalyst and substrate through multiple recognition in a confined environment [20]. Compared to monotopic β-CD, the closeness of the involved entities in the surrounding of the dipotic β-CD platform greatly enhanced both the conversion and the chemoselectivity in Rh-catalyzed HF of 1-decene.…”

Section: Cd-based Organometallic Catalysts Self-assembled Via Hydrophmentioning

confidence: 99%

Unconventional Approaches Involving Cyclodextrin-Based, Self-Assembly-Driven Processes for the Conversion of Organic Substrates in Aqueous Biphasic Catalysis

Hapiot

Monflier

2017

Catalysts

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Abstract:Aqueous biphasic catalysis is a convenient approach to convert organic, partially soluble molecules in water. However, converting more hydrophobic substrates is much more challenging as their solubility in water is extremely low. During the past ten years, substantial progress has been made towards improving the contact between hydrophobic substrates and a hydrophilic transition-metal catalyst. The main cutting-edge approaches developed in the field by using cyclodextrins as a supramolecular tool will be discussed and compared in this short review.

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“…29,30 In these systems, the cavity only encapsulates an appropriate ligand and helps the metal ion to sit at its edge. 31 The catalyst is a rhodium phosphine complex formed by complexation of the Rh(I) ion to a phosphine ligand bearing a biphenyl moiety prone to β-CD encapsulation. The same group recently synthesized a CD dimer aimed at simultaneously hosting the substrate and the catalyst in each cavity (Figure 13).…”

Section: Water-solubilization Of a Complex Through Ligand Hosting In mentioning

confidence: 99%

Supramolecular control of transition metal complexes in water by a hydrophobic cavity: a bio-inspired strategy

Bistri

Reinaud

2015

Org. Biomol. Chem.

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Supramolecular chemistry in water is a very challenging research area. In biology, water is the universal solvent where transition metal ions play major roles in molecular recognition and catalysis. In enzymes, it participates in substrate binding and/or activation in the heart of a pocket defined by the folded protein. The association of a hydrophobic cavity with a transition metal ion is thus a very appealing strategy for controlling the metal ion properties in the very competitive water solvent. Various systems based on intrinsically water-soluble macrocyclic structures such as cyclodextrins, cucurbituryls, and metallo-cages have been reported. Others use calixarenes and resorcinarenes functionalized with hydrophilic substituents. One approach for connecting a metal complex to these cavities is to graft a ligand for metal ion binding at their edge. Early work with cyclodextrins has shown Michaelis-Menten like catalysis displaying enhanced kinetics and substrate-selectivity. Remarkable examples of regio- and stereo-selective transformation of substrates have been reported as well. Dynamic two-phase systems for transition metal catalysis have also been developed. They rely on either water-transfer of the metal complex through ligand embedment or synergistic coordination of a metal ion and substrate hosting. Another strategy consists in using metallo-cages, which provide a well-defined hydrophobic space, to stabilize metal complexes in water. When the cages can host simultaneously a substrate and a reactive metal complex, size- and regio-selective catalysis was obtained. Finally, construction of a polydentate coordination site closely interlocked with a calixarene or resorcinarene macrocycle has been shown to be a very fruitful strategy for obtaining metal complexes with remarkable hosting properties. For each of these systems, the synergism resulting from the biomimetic association of a hydrophobic cavity and a metal ion is discussed within the objective of developing new tools for either selective molecular recognition (with analytical perspectives) or performant catalysis, in water.

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A cyclodextrin dimer as a supramolecular reaction platform for aqueous organometallic catalysis

Abstract: A reaction platform based on a cyclodextrin dimer, which is able to simultaneously include a substrate in one cavity and an organometallic catalyst into the other, proved to be highly efficient for aqueous hydroformylation reaction of higher olefins.

Cited by 28 publications

References 43 publications

Method of Continuous Variations: Applications of Job Plots to the Study of Molecular Associations in Organometallic Chemistry

Method of Continuous Variations: Applications of Job Plots to the Study of Molecular Associations in Organometallic Chemistry

Unconventional Approaches Involving Cyclodextrin-Based, Self-Assembly-Driven Processes for the Conversion of Organic Substrates in Aqueous Biphasic Catalysis

Supramolecular control of transition metal complexes in water by a hydrophobic cavity: a bio-inspired strategy

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