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

Breuil, Pierre‐Alain R.; Patureau, Frédéric W.; Reek, Joost N. H.

doi:10.1002/anie.200806177

Cited by 119 publications

(75 citation statements)

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“…[8] This complex affords the highest enantioselectivity (> 99 % ee)reported up to now for the hydrogenation of methyl 2-hydroxymethacrylate (and several of its derivatives), which upon hydrogenation forms the so-called "Roche ester", an important intermediate in the preparation of several biologically active compounds.C atalScheme 1. The chemical structures of the ligand building blocks with H-bond acceptors (L1-L4)a nd H-bond donor (L5), and atypical example of aself-assembled bidentatel igands around arhodium complex (6).…”

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confidence: 91%

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Rational Optimization of Supramolecular Catalysts for the Rhodium‐Catalyzed Asymmetric Hydrogenation Reaction

et al. 2017

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Rational design of catalysts for asymmetric transformations is alongstanding challenge in the field of catalysis. In the current contribution we report ac atalyst in which ah ydrogen bond between the substrate and the catalyst plays ac rucial role in determining the selectivity and the rate of the catalytic hydrogenation reaction, as is evident from ac ombination of experiments and DFT calculations.D etailed insight allowed in silico mutation of the catalyst such that only this hydrogen bond interaction is stronger,p redicting that the new catalyst is faster.I ndeed, we experimentally confirmed that optimization of the catalyst can be realized by increasing the hydrogen bond strength of this interaction by going from aurea to phosphine oxide H-bond acceptor on the ligand.The asymmetric hydrogenation reaction is undoubtedly the most powerful asymmetric transformation for the fine chemical industry as it provides ar ather general strategy to create chiral centers in organic molecules.[1] As the synthesis of the desired products cannot always be reached using the existing catalysts,t he search for new methods and concepts has received considerable attention.[2] Combinatorial chemistry approaches and high-throughput catalyst screenings have been demonstrated to be increasingly important.[3] Fort he generation of catalyst libraries based on chiral ligands,the use of supramolecular ligand building blocks that form bidentate ligands by self-assembly is apowerful strategy as the number of catalysts grows exponentially with the number of synthesized building blocks. [4] Next to interactions between the two ligand building blocks,hydrogen bonding between functional groups of the substrate and the ligands at the metal complex can contribute to catalyst selectivity.[5] One of the major goals in the area of asymmetric hydrogenation, or more general in the field of catalysis,would be the rational design of transition metal catalysts.Although for several catalyst systems detailed knowledge on the reaction mechanism has been obtained, [6] prediction of the catalyst properties is still very challenging. [7] However,w hen the selectivity of ac atalytic reaction is controlled by supramolecular interactions,f urther rational optimization could be performed, guided by theoretical prediction. Herein we report the first example of rational design of ac atalyst for the asymmetric hydrogenation reaction by optimization of the supramolecular interactions between the substrate and the catalyst, leading to enhanced activity and superior selectivity in the hydrogenation of hydroxy-functionalized di-and trisubstituted alkenes.I n order to allow ar ational approach, the reaction mechanism of the supramolecular catalyst used was investigated by means of X-ray crystallography,N MR spectroscopy,k inetic studies,a nd DFT calculations of the reaction pathway. Subsequently,t he relevant supramolecular interactions between the substrate and the catalyst were optimized in silico,r esulting in the rational design of as econd generation of ca...

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“…[8] Instead, the OH group inserts in the existing hydrogen bond between L1 and L5,l eading to the formation of two hydrogen bonds between the substrate and the complex (Figure 1). This complex was found to be 5.45 kcal mol À1 more stable than the alternative complexes that were computed, and as such is the major catalystsubstrate species observed in solution.…”

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Rational Optimization of Supramolecular Catalysts for the Rhodium‐Catalyzed Asymmetric Hydrogenation Reaction

et al. 2017

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“…For instance, the elegant systems employed by the group of Jun [94] and Breit et al, [95] wherein the ligand interacts strongly with the substrate of choice -be it an aldehyde to infer selective hydroacylation, through the formation of a reversible imine bond, or the hydroformylation of α,β-unsaturated carboxylic acids, making use of directing H-bonding -have been tested mainly with Rh and Ru. Related approaches using bifunctional substrate activation have been developed by Reek et al, wherein hydrogen bonding interactions [96] between the ligands and the substrates were shown to enhance the asymmetric hydrogenation of functionalized substrates. The use of an anion-binding pocket as the backbone of a diphosphorus ligand was able to regulate the regioselectivity during the rhodium-catalyzed hydroformylation of unsaturated carboxylate substrates.…”

Section: Supramolecular Cooperative Catalysismentioning

confidence: 98%

Cooperative Catalysis with First‐Row Late Transition Metals

2011

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Cooperative catalysis with first-row transition metals holds much promise for future developments regarding sustainable, selective transformations, including e.g. alkenes, dienes and a variety of small molecules such as CO 2 , N 2 and water. This non-exhaustive analysis of the current state-ofthe-art aims to give a comprehensive overview of the various design strategies and applications of first-row transition metal cooperative reactivity and to provide leads for new research initiatives in order to expand this emerging field. The

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“…74 Interestingly, Reek and coworkers have also reported the generation of heterodimeric supramolecular complexes by hydrogenbonding-mediated assembly of a phosphoramidite, which is a good hydrogen bond donor, and the urea carbonyl group, in the presence of a rhodium precursor. 75 NMR studies revealed that the heterodimeric complex 62 ( Figure 5) was the only complex that was formed (>99% purity). The authors then assayed the heterodimeric complex 62 in the rhodium-mediated asymmetric hydrogenation of methyl 2-(hydroxymethyl) acrylate (Roche's ester).…”

Section: Use Of Hydrogen Bonding In the Construction Of The Catalyst mentioning

confidence: 99%

Supramolecular Catalysis

Ballester¹,

Leeuwer²,

Vidal-Ferran³

2015

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

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

Cited by 119 publications

References 65 publications

Rational Optimization of Supramolecular Catalysts for the Rhodium‐Catalyzed Asymmetric Hydrogenation Reaction

Rational Optimization of Supramolecular Catalysts for the Rhodium‐Catalyzed Asymmetric Hydrogenation Reaction

Cooperative Catalysis with First‐Row Late Transition Metals

Supramolecular Catalysis

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