Design and Assembly of a Chiral Metallosalen‐Based Octahedral Coordination Cage for Supramolecular Asymmetric Catalysis

Tan, Chunxia; Jiao, Jingjing; Li, Zijian; Liu, Yan; Han, Xing; Cui, Yong

doi:10.1002/anie.201711310

Cited by 195 publications

(125 citation statements)

References 70 publications

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“…In this case again, the incorporated metal‐salen complexes showed improved activity and selectivity compared to the homogeneous catalysts thanks to encapsulation and concentration of the reactants, and tandem reactions with the mixed cages containing Mn‐ and Cr‐salen species yielded up to 99.9 % ee for asymmetric alkene epoxidation followed by sequential epoxide ring‐opening. Another example was reported by the same group, in which Mn‐salen complexes were used as building struts for the assembly of an octahedral coordination cage from calixarenes, as proved by X‐ray diffraction analysis . This enantiopure Mn‐bearing cage was a very efficient catalyst to promote the oxidative kinetic resolution of racemic secondary alcohols.…”

Section: Salen Immobilized On Mofs and Cofsmentioning

confidence: 91%

Chiral Salen Complexes for Asymmetric Heterogeneous Catalysis: Recent Examples for Recycling and Cooperativity

2019

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Chiral salen complexes are privileged and versatile catalysts used in a wide variety of enantioselective transformations. Researches for their use in multicatalysis, including cooperative as well as tandem processes, are more recent, but many reports already highlight the important effect of the salen ligand structure on reaction rates and/or selectivities. This review article thus outlines the literature covering last five years, on the current developments of chiral polymetallic salen complexes used in asymmetric heterogeneous catalysis; their preparation, their efficiency as catalysts in various reactions and their recyclability are highlighted according to the immobilization procedures involved for their heterogenization. These methods include grafting on organic or inorganic supports insuring easy recovery by simple filtration. Polymerization processes are also part of recent research, leading to high densities of catalytic sites to favor their cooperativity. Combination of salen complexes via non covalent interactions or their introduction on MOFs and COFs networks is currently in full expansion, with examples of highly functionalized and enantioenriched products issued from tandem catalysis.

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Section: Salen Immobilized On Mofs and Cofsmentioning

confidence: 91%

Chiral Salen Complexes for Asymmetric Heterogeneous Catalysis: Recent Examples for Recycling and Cooperativity

2019

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“…Adopting the concept of using privileged ligands to make chiral metal–organic frameworks (MOFs), Cui and co‐workers recently extended this strategy to synthesize a chiral octahedral coordination cage ( cage 6 ), which was constructed by using 12 enantiopure Mn(salen)‐derived dicarboxylic acids ( L 6 ) as linear linkers and six Zn 4 ‐ p‐tert ‐butylsulfonylcalix[4]arene clusters as tetravalent four‐connected vertices (Figure ) . Because the large hydrophobic cavity (≈3944 Å 3 ) of the porous cage is decorated with catalytically active metallosalen moieties, it can efficiently catalyze the OKR of racemic secondary alcohols with up to 99.3 % ee and k rel =35.0.…”

Section: Immobilization Of Catalytic Active Sites On Cages For Asymmementioning

confidence: 99%

“…2) Embedded catalysts for asymmetric catalysis; chiral catalysts are directly embedded inside the cage to work synergistically with the confined cavity. 3) Immobilization of catalytic sites on cages for asymmetric catalysis; the catalytic sites are either incorporated into enantiopure bridging ligands or introduced as metal nodes that are connected to and surrounded by chiral auxiliary ligands. Specific examples are selected to elucidate the related approach in each section, and the final section briefly presents conclusions and perspectives for future development.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Coordination Cages for Asymmetric Catalysis

Tan

Chu

Tang

et al. 2018

Chemistry A European J

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152

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Inspired by the high efficiency and specificity of enzymes in living systems, the development of artificial catalysts intrinsic to the key features of enzyme has emerged as an active field. Recent advances in supramolecular chemistry have shown that supramolecular coordination cages, built from non-covalent coordination bonds, offer a diverse platform for enzyme mimics. Their inherent confined cavity, analogous to the binding pocket of an enzyme, and the facile tunability of building blocks are essential for substrate recognition, transition-state stabilization, and product release. In particular, the combination of chirality with supramolecular coordination cages will undoubtedly create an asymmetric microenvironment for promoting enantioselective transformation, thus providing not only a way to make synthetically useful asymmetric catalysts, but also a model to gain a better understanding for the fundamental principles of enzymatic catalysis in a chiral environment. The focus here is on recent progress of supramolecular coordination cages for asymmetric catalysis, and based on how supramolecular coordination cages function as reaction vessels, three approaches have been demonstrated. The aim of this review is to offer researchers general guidance and insight into the rational design of sophisticated cage containers for asymmetric catalysis.

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“…Complementary to the above MOCs with chiral confined microenvironment or cooperative chiral catalytic sites immobilized in their cavities, the direct introduction of effective privileged ligands and/or metal vertices with chiral catalytic active sites can also generate cages that can catalyze a variety of asymmetric transformations. Following these principles, Cui and co‐workers recently constructed a chiral octahedral coordination cage ( C5 ) using 12 enantiopure Mn(salen)‐derived dicarboxylic acids ( L 5 ‐Mn) as linear linkers and six Zn 4 ‐ p ‐ tert ‐butylsulfonylcalix[4]arene clusters as tetravalent four‐connected vertices ( Figure a). This functionalized porous cage features a very large hydrophobic chiral cavity (≈3944 Å 3 ) decorated with catalytically active chiral metallosalen species, allowing the cage to serve as an efficient asymmetric catalyst for the oxidative kinetic resolution (OKR) of racemic secondary alcohols and the epoxidation of olefins with up to >99% enantiomeric excess (Figure b).…”

Section: Asymmetric Catalysis Within the Chiral Confined Space Of Mocsmentioning

confidence: 99%

Section: Asymmetric Catalysis Within the Chiral Confined Space Of Mocsmentioning

confidence: 99%

Asymmetric Catalysis within the Chiral Confined Space of Metal–Organic Architectures

Cheng

et al. 2019

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The effective synthesis of chiral compounds in a highly enantioselective manner is obviously attractive. Inspired by the enzymatic reactions that occur in pocket‐like cavities with high efficiency and specificity, chemists are seeking to construct catalysts that mimic this key feature of enzymes. Recent progress in supramolecular coordination chemistry has shown that metal–organic cages (MOCs) and metal–organic frameworks (MOFs) with chiral confined cavities/pores may offer a novel platform for achieving asymmetric catalysis with high enantioselectivity. The inherent chiral confined microenvironment is considered to be analogous to the binding pocket of enzymes, and this pocket promotes enantioselective transformations. This work focuses on the recent advances in MOCs and MOFs with chiral confined spaces for asymmetric catalysis, and each section is separated into two parts based on how the chirality is achieved in these metal–organic architectures. A special emphasis is placed on discussing the relationship between the enantioselectivity and the confined spaces of the chiral functional MOCs and MOFs rather than catalytic chemistry. Finally, current challenges and perspectives are discussed. This work is anticipated to offer researchers insights into the design of sophisticated chiral confined space‐based metal–organic architectures for asymmetric catalysis with high enantioselectivity.

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Design and Assembly of a Chiral Metallosalen‐Based Octahedral Coordination Cage for Supramolecular Asymmetric Catalysis

Cited by 195 publications

References 70 publications

Chiral Salen Complexes for Asymmetric Heterogeneous Catalysis: Recent Examples for Recycling and Cooperativity

Chiral Salen Complexes for Asymmetric Heterogeneous Catalysis: Recent Examples for Recycling and Cooperativity

Supramolecular Coordination Cages for Asymmetric Catalysis

Asymmetric Catalysis within the Chiral Confined Space of Metal–Organic Architectures

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