Modulating the catalytic activity by the mechanical bond: organocatalysis with polyamide [2]rotaxanes bearing a secondary amino function at the thread

Perez, Jesus de Maria; Alajarı́n, Mateo; Martínez-Cuezva, Alberto; Berná, José

doi:10.1039/d2qo00481j

Cited by 5 publications

(2 citation statements)

References 52 publications

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“…10 As a result, the hydrogen-bonding ability of these units with the embedded binding sites is adjusted, leading to variations in the internal rotational and translational motions. 11 Moreover, in this way the stability of the mechanical bond in kinetically stable [2]pseudorotaxanes can also be altered. 12 It is worth noting that despite these strategies based on the electronic effects of substituents, other structural modifications of the macrocyclic component to modulate the internal dynamics in hydrogen-bonded [2]rotaxanes remains relatively unexplored.…”

Section: Introductionmentioning

confidence: 99%

Modulating the shuttling motion of [2]rotaxanes built of p-xylylenediamine units through permethylation at the benzylic positions of the ring

Puigcerver,

Alajarin,

Martinez-Cuezva

et al. 2023

Org. Biomol. Chem.

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Section: Introductionmentioning

confidence: 99%

Modulating the shuttling motion of [2]rotaxanes built of p-xylylenediamine units through permethylation at the benzylic positions of the ring

Puigcerver,

Alajarin,

Martinez-Cuezva

et al. 2023

Org. Biomol. Chem.

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“…Additionally, the stabilizing effect of the macrocycle when placed over different functional groups at the thread, coupled with the relative movement of the two components, makes rotaxanes ideal candidates for designing switchable catalysts by facilitating both activation or deactivation of catalytic sites (ON/OFF) or the selection of different activation modes . Recent investigations have demonstrated that organocatalysts embedded in [2]rotaxane architectures with benzylic amide-based macrocycles show no decrease in their catalytic activity, but instead, the mechanical bond enhances the efficiency of the interlocked catalyst …”

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confidence: 99%

Urea-Based [2]Rotaxanes as Effective Phase-Transfer Organocatalysts: Hydrogen-Bonding Cooperative Activation Enabled by the Mechanical Bond

Puigcerver,

Zamora-Gallego,

Marin-Luna

et al. 2024

J. Am. Chem. Soc.

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We finely designed a set of [2]rotaxanes with urea threads and tested them as hydrogen-bonding phase-transfer catalysts in two different nucleophilic substitutions requiring the activation of the reactant fluoride anion. The [2]rotaxane bearing a fluorinated macrocycle and a fluorine-containing urea thread displayed significantly enhanced catalytic activity in comparison with the combination of both noninterlocked components. This fact highlights the notably beneficial role of the mechanical bond, cooperatively activating the processes through hydrogen-bonding interactions.

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Formation and Stability of Benzylic Amide [2]‐ and [3]Rotaxanes: An Intercomponent Interactions Study

Orlando,

Weimer,

Salbego

et al. 2024

Chemistry A European J

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One of the most recent focuses in supramolecular chemistry is developing molecules designed to exhibit programmable properties at the molecular level. Rotaxanes, which function as molecular machines with movements controlled by external stimuli, are prime candidates for this purpose. However, the controlled synthesis of rotaxanes, especially amide‐benzylic rotaxanes with more than two components, remains an area ripe for exploration. In this study, we aim to elucidate the formation of amide‐benzylic [3]rotaxanes using a thread that includes a conventional succinamide station and an innovative triazole‐carbonyl station. Including the triazole‐carbonyl station introduces new perspectives into the chemistry of rotaxanes, influencing their conformation and dynamics. The synthesis of two‐station rotaxanes with varying stoppers demonstrated that the macrocycle consistently occupies the succinamide station, providing greater stability as evidenced by NMR and SC‐XRD analyses. The presence of a triazole‐carbonyl station facilitated the formation of a second macrocycle exclusively when a secondary amide was employed as the stopper group, presumably due to decreased steric hindrance. Moreover, the second macrocycle directly forms at the triazole‐carbonyl station. This investigation reveals that slight modifications in the thread structure can dramatically impact the formation, stability, and interactions between components of rotaxanes.

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Modulating the catalytic activity by the mechanical bond: organocatalysis with polyamide [2]rotaxanes bearing a secondary amino function at the thread

Abstract: The modulation of the catalytic activity of degenerate succinamide-based [2]rotaxanes by changes at their macrocyclic component is disclosed herein. These systems, bearing an acyclic secondary amine function at the thread...

Cited by 5 publications

References 52 publications

Modulating the shuttling motion of [2]rotaxanes built of p-xylylenediamine units through permethylation at the benzylic positions of the ring

Modulating the shuttling motion of [2]rotaxanes built of p-xylylenediamine units through permethylation at the benzylic positions of the ring

Urea-Based [2]Rotaxanes as Effective Phase-Transfer Organocatalysts: Hydrogen-Bonding Cooperative Activation Enabled by the Mechanical Bond

Formation and Stability of Benzylic Amide [2]‐ and [3]Rotaxanes: An Intercomponent Interactions Study

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