Interlocking the Catalyst: Thread versus Rotaxane-Mediated Enantiodivergent Michael Addition of Ketones to β-Nitrostyrene

Martínez-Cuezva, Alberto; Marín‐Luna, Marta; Alonso, Diego A.; Ros-Ñiguez, Diego; Alajarı́n, Mateo; Berná, José

doi:10.1021/acs.orglett.9b01791

Cited by 42 publications

(19 citation statements)

References 53 publications

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“…[21] In this chapter, we will focus on those examples where the macrocyclic unit of an interlocked catalyst actively participates in the catalytic reaction. Thus, we will not cover examples where the macrocycle is introduced for other purposes, such as the introduction/enhancement of chiral information [22] or the blocking/deblocking [23] of a catalytically active group.…”

Section: Mechanically Interlocked Macrocyclic Organocatalystsmentioning

confidence: 99%

Functionalized Macrocycles in Supramolecular Organocatalysis

Kauerhof

Niemeyer

2020

ChemPlusChem

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Supramolecular organocatalysis has emerged as a novel research field in the context of homogeneous catalysis. In particular, the use of functionalized macrocycles as supramolecular catalysts is highly promising, as these systems are oftentimes easily accessible and offer distinct advantages in catalysis. Macrocyclic catalysts can provide defined binding pockets, such as hydrophobic cavities, and can thus create a reaction microenvironment for catalysis. In addition, macrocycles can offer a preorganized arrangement of functional groups, such as binding sites or catalytically active groups, thus enabling a defined and possibly multivalent binding and activation of substrates. The aim of this Minireview is to provide an overview of recent advances in the area of supramolecular organocatalysis based on functionalized macrocycles (including cyclodextrins, calixarenes, and resorcinarenes), with a focus on those examples where certain catalytically active groups (such as hydrogen bond donors/acceptors, Brønsted acid or base groups, or nucleophilic units) are present in or have been installed on the macrocycles.

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Section: Mechanically Interlocked Macrocyclic Organocatalystsmentioning

confidence: 99%

Functionalized Macrocycles in Supramolecular Organocatalysis

Kauerhof

Niemeyer

2020

ChemPlusChem

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“…[6] In transition-metal catalysis,L eigh used rotaxanes with chiral diamine-based macrocycles for Ni-catalyzed enantioselective Michael additions, [7] while Goldup employed mechanically planar-chiral rotaxane ligands for Au-mediated cyclopropanations. [8] In the realm of organocatalysis,L eigh and Berna developed rotaxanes featuring nucleophilic secondary amines on the axle.M aking use of either stereogenic centers in close vicinity to the amine [9] or by employing the macrocycle to achieve ad esymmetrization of a( pseudo)symmetric thread, [10] these rotaxane catalysts were applied for enantioselective Michael additions or a-functionalizations.…”

Section: Introductionmentioning

confidence: 99%

Heterobifunctional Rotaxanes for Asymmetric Catalysis

et al. 2020

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Heterobifunctional rotaxanes serve as efficient catalysts for the addition of malonates to Michael acceptors. We report a series of four different heterobifunctional rotaxanes, featuring an amine‐based thread and a chiral 1,1′‐binaphthyl‐phosphoric‐acid‐based macrocycle. High‐level DFT calculations provided mechanistic insights and enabled rational catalyst improvements, leading to interlocked catalysts that surpass their non‐interlocked counterparts in terms of reaction rates and stereoselectivities.

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“…Taking into account the utmost importance of chirality in chemistry and other sciences, it is not surprising that the synthesis, study, and applications of chiral rotaxanes and catenanes has recently started to increasingly attract attention. 11 In this sense, the introduction of chiral stereogenic elements, 12 that is, chiral covalent stereogenic centers, chiral stereogenic axis, mechanical planar chirality, 13 or co-conformational covalent or planar chirality, 14 led to interesting applications based precisely on the presence of chirality, such as asymmetric catalysis, 15 chiral anion recognition, 16 or molecular information ratchets. 14a , 14b…”

Section: Introductionmentioning

confidence: 99%

A [2]Rotaxane-Based Circularly Polarized Luminescence Switch

et al. 2019

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A rotaxane-based molecular shuttle has been synthesized in which the switching of the position of a fluorescent macrocycle on the thread turns “on” or “off” the circularly polarized luminescence (CPL) of the system while maintaining similar fluorescence profiles and quantum yields in both states. The chiroptical activity relies on the chiral information transfer from an ammonium salt incorporating d - or l -phenylalanine residues as chiral stereogenic covalent units to an otherwise achiral crown ether macrocycle bearing a luminescent 2,2′-bipyrene unit when they interact through hydrogen bonding. Each enantiomeric thread induces CPL responses of opposite signs on the macrocycle. Upon addition of base, the switching of the position of the macrocycle to a triazolium group disables the chiral information transfer to the macrocycle, switching “off” the CPL response. The in situ switching upon several acid/base cycles is also demonstrated.

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Interlocking the Catalyst: Thread versus Rotaxane-Mediated Enantiodivergent Michael Addition of Ketones to β-Nitrostyrene

Cited by 42 publications

References 53 publications

Functionalized Macrocycles in Supramolecular Organocatalysis

Functionalized Macrocycles in Supramolecular Organocatalysis

Heterobifunctional Rotaxanes for Asymmetric Catalysis

A [2]Rotaxane-Based Circularly Polarized Luminescence Switch

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