Libraries of Bidentate Phosphorus Ligands; Synthesis Strategies and Application in Catalysis

Goudriaan, P. Elsbeth; Leeuwen, Piet W. N. M. van; Birkholz, Mandy‐Nicole; Reek, Joost N. H.

doi:10.1002/ejic.200800139

Cited by 103 publications

(37 citation statements)

References 96 publications

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“…For these challenging reactions, the trial-and-error approach is still dominant in the search for appropriate catalysts, and thus, combinatorial methods and high-throughput screening of ligands and catalysts have been developed. [2] Supramolecular ligands that form by selfassembly of smaller components appear suitable for this approach, as the modular synthesis efficiently generates wide libraries of ligands. [3] Enzyme mimicry represents an alternative route to selective catalysts.…”

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“…In the absence of a phosphorus ligand, substrate 5 is hydroformylated with poor selectivity (l/b = 1.8) and low convrsion (Table 1, entry 4). Importantly, for non-anionic substrates, the addition of excess acetate ion that binds in the DIM pocket of [Rh(1)(CO) 2 H] has no effect on the (low) regioselectivity. [17] The substrates that are longer than the one that precisely fits between the metal and the binding site-5-hexenoate through 8-nonenoate anion-also experience an effect of binding in the DIM pocket.…”

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Remote Supramolecular Control of Catalyst Selectivity in the Hydroformylation of Alkenes

et al. 2011

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Dedicated to Professor Janusz Jurczak on the occasion of his 70th birthdayImmense progress in the field of transition-metal catalysis has been achieved over the past few decades, and the contributions of the ligands that are coordinated to the metals are now well understood.[1] Despite notable insights made into various reaction mechanisms, the prediction of the selectivity that a new catalyst will display is still beyond our abilities. This becomes a particularly difficult issue when the reaction pathways that lead to the isomeric products are nearly identical in energy, or worse, if the pathway to the desired isomer is higher in energy. For these challenging reactions, the trial-and-error approach is still dominant in the search for appropriate catalysts, and thus, combinatorial methods and high-throughput screening of ligands and catalysts have been developed.[2] Supramolecular ligands that form by selfassembly of smaller components appear suitable for this approach, as the modular synthesis efficiently generates wide libraries of ligands. [3] Enzyme mimicry represents an alternative route to selective catalysts. Inspired by the properties and working principles of enzymes, a great effort in catalyst development has been applied to the incorporation of cavitands that can bind guest molecules to an active site and promote reactions that are typically displayed by enzymes.[4] Remarkable examples of highly selective oxidation reactions catalyzed by metalloporphyrins, where hydrophobic interactions allow for substrate preorganization, have been developed by Breslow and co-workers.[5] However, simple hydrogen-bonding interactions between a substrate and the functional groups of a catalyst can also be used to greatly improve the selectivity of a reaction. This principle was elegantly demonstrated by Crabtree, Brudvig, and co-workers in a dimanganese catalyst for the highly selective functionalization of C À H bonds at sp 3 -hybridized carbon atoms. [6] Recently, our research group showed that even a single hydrogen bond between a catalyst and a substrate leads to improved activities in cyclopropanation reactions, [7] and excellent enantioselectivity in the hydrogenation of the Roche ester precursor.[8] A similar supramolecular substrate preorganization strategy has been reported by Breit and co-workers, who applied guanidinium-functionalized phosphines to the regioselective hydroformylation of vinylacetic acid and its analogues. [9] As supramolecular interactions can be arranged relatively easily, selective installation of functional groups can provide a powerful tool for the rational design of selective catalysts that operate predicatively. The approach requires a set of receptors that can address a wide range of functional groups. In addition, the impact would be larger if the selectivity could also be controlled by noncovalent interactions that are more remote from the catalytic center. Herein we report a bisphosphine ligand based on an anion receptor backbone. As predicted, the ligand can be used in a regioselec...

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Remote Supramolecular Control of Catalyst Selectivity in the Hydroformylation of Alkenes

et al. 2011

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“…For asymmetric catalysis, however, catalyst optimization relies to a large extent on trial and error, hence the combinatorial screening of libraries of chiral catalysts is a frequently applied strategy. [1] Besides catalyst screening, attempts toward the rational design of chiral catalysts have also been made, which generally lead to strategies for ligand development. [2] The asymmetric hydrogenation reaction is among the classic success stories in this respect since it has resulted in several scientific breakthroughs, [3] as well as the development of commercial processes.…”

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Singly Hydrogen Bonded Supramolecular Ligands for Highly Selective Rhodium‐Catalyzed Hydrogenation Reactions

2009

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H bonds make the catalysts! A single hydrogen bond between ligands coordinated to a rhodium center is critical for the formation of pure supramolecular catalysts for asymmetric hydrogenation reactions. The ester group of the amidite ligand (see scheme) also forms a hydrogen bond with the coordinated substrate. Use of the heterocomplex afforded the highest enantioselectivity reported to date for the hydrogenation of several ester substrates.

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“…Systems based on bidentate phosphorus ligands have been shown to be highly successful in asymmetric transition-metal catalysis [18,19], but efficient combinatorial methodologies to facilitate the synthesis and screening of vast libraries of these type of ligands are still lacking. This is mainly due to laborious (and low yielding) work-up procedures of these type of compounds and their sensitivity towards moisture and air [20].…”

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Solid-Phase Synthesis and Catalytic Screening of Polystyrene Supported Diphosphines

et al. 2016

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Libraries of Bidentate Phosphorus Ligands; Synthesis Strategies and Application in Catalysis

Cited by 103 publications

References 96 publications

Remote Supramolecular Control of Catalyst Selectivity in the Hydroformylation of Alkenes

Remote Supramolecular Control of Catalyst Selectivity in the Hydroformylation of Alkenes

Singly Hydrogen Bonded Supramolecular Ligands for Highly Selective Rhodium‐Catalyzed Hydrogenation Reactions

Solid-Phase Synthesis and Catalytic Screening of Polystyrene Supported Diphosphines

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