Interplay between a Foldamer Helix and a Macrocycle in a Foldarotaxane Architecture

Gauthier, Maxime; Koehler, Victor; Clavel, Caroline; Kauffmann, Brice; Huc, Ivan; Ferrand, Yann; Coutrot, Frédéric

doi:10.1002/anie.202100349

Cited by 16 publications

(8 citation statements)

References 71 publications

(7 reference statements)

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“…Recently, we reported the formation of a foldarotaxane architecture consisting in a [2]rotaxane, the axle of which is also wrapped by a foldamer helix. 12 We showed that the winding of the helix around the encircled axle can be altered by the macrocycle localisation. Here, we investigate the reciprocal effect.…”

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confidence: 87%

[3]Foldarotaxane-mediated synthesis of an improbable [2]rotaxane

et al. 2022

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confidence: 87%

[3]Foldarotaxane-mediated synthesis of an improbable [2]rotaxane

et al. 2022

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“…Recent works exploited the fact that alkyl-carbamate rods that form foldaxanes may themselves be rotaxanes. 64 For instance, [2]rotaxane 20 (Figure 8C) possesses a dicarbamate binding station on which a helical foldamer may wind. It also contains an ammonium group as a binding site for a dibenzo-24-crown-8 (DB24C8) macrocycle.…”

Section: Effect Of Foldaxane Formation On Rodmentioning

confidence: 99%

Foldaxanes: Rotaxane-like Architectures from Foldamers

et al. 2022

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Conspectus Mechanically interlocked molecules such as rotaxanes and catenanes contain free-moving components that cannot dissociate and have enabled the investigation and control of various translational and rotational molecular motions. The architecture of pseudo-rotaxanes and of some kinetically labile rotaxanes is comparable to that of rotaxanes but their components are reversibly associated and not irreversibly interlocked. In other words, pseudo-rotaxanes may fall apart. This Account focuses on a peculiar family of rotaxane-like architectures termed foldaxanes. Foldaxanes consist of a helically folded oligomer wound around a rod-like dumbbell-shaped guest. Winding of the helix around the rod thus entails an unwinding–rewinding process that creates a kinetic barrier. It follows that foldaxanes, albeit reversibly assembled, have significant lifetimes and may not fall apart while defined molecular motions are triggered. Foldaxanes based on helically folded aromatic oligoamide hosts and oligo(alkyl carbamate) guests can be designed rationally through the inclusion of complementary binding motifs on the rod and at the inner rim of the helix so that helix length and rod length match. Single helical foldaxanes (bimolecular species) and double helical foldaxanes (trimolecular species) have thus been produced as well as poly[n]foldaxanes, in which several helices bind to long rods with multiple binding stations. When the binding stations differ and are organized in a certain sequence, a complementary sequence of different stacked helices, each matching with their binding station, can be assembled, thus reproducing in an artificial system a sort of translation process. Foldaxane helix handedness may be controlled by stereogenic centers on the rod-like guest. Handedness can also be transmitted from helix to helix in polyfoldaxanes. Foldaxane formation has drastic consequences for the rod properties, including its stiffening and the restriction of the mobility of a macrocycle already interlocked on the rod. Fast translation (without dissociation) of helices along rod-like guests has been demonstrated. Because of the helical nature of the hosts, translation may be accompanied by rotation in various sorts of screw-like motions. The possibility, on longer time scales, for the helix to dissociate from and reassociate to the rod has allowed for the design of complex, kinetically controlled supramolecular pathways of a helix on a rod. Furthermore, the design of helices with a directionality, that is, with two distinct termini, that bind to nonsymmetrical rod-like guests in a defined orientation makes it possible to also control the orientation of molecular motion. Altogether, foldaxanes constitute a distinct and full-of-potential family of rotaxane-like architectures that possess designer structures and allow orchestration of the time scales of various supramolecular events.

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“…In the past years, we have been focusing on the synthesis of several DB24C8‐based rotaxane molecular shuttles based on triazolium, [9] pyridinium amide, [10] amide, [11] Weinreb amide, [5b,d] amine and ketone [5d] moieties as more or less efficient secondary molecular stations for the DB24C8. Recently, we proposed the N ‐hydroxysuccinimide [5a,12] (NHS) and its NHS ester derivative [11,13] as thread's pseudo stoppers that allowed slippage of the DB24C8, on the one hand, and subsequent post‐synthetic [14] stopper exchange [5a,c,12a–b,13a,15] of rotaxane threads on the other hand. More precisely, NHS ester rotaxane building block was utilized as a precursor of a two‐station molecular shuttle containing a triazolium secondary station for the DB24C8 [13a] .…”

Section: Introductionmentioning

confidence: 99%

“…The control of the localization of the macrocycle along the encircled thread may be possible if the affinities between stations and macrocycle are different. Altering the affinities through chemical or physical stimuli , [6] or destabilizing a station‐macrocycle complex through intermolecular interaction, [5c,7] afforded a wide range of responsive rotaxanes molecular shuttles in the literature until now, with multiple miscellaneous applications [8] . In the past years, we have been focusing on the synthesis of several DB24C8‐based rotaxane molecular shuttles based on triazolium, [9] pyridinium amide, [10] amide, [11] Weinreb amide, [5b,d] amine and ketone [5d] moieties as more or less efficient secondary molecular stations for the DB24C8.…”

Section: Introductionmentioning

confidence: 99%

Study of [2]‐ and [3]Rotaxanes Obtained by Post‐Synthetic Aminolysis of a Kinetically Stable Carbonate‐Containing Pseudorotaxane

2022

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Here is reported the synthesis and study of dibenzo‐24‐crown‐8 (DB24C8)‐based [2]‐ and [3]rotaxanes that contain an ammonium as the best molecular station and carbamate moieties as secondary molecular stations. The common post‐interlocking synthesis relies on the aminolysis of the N‐succinimidyl carbonate extremity of an activated though insulated pseudorotaxane. The N‐succinimidyl carbonate‐based thread's extremity proved to be small enough to allow the slow slippage of the DB24C8 around the thread and large enough to allow insulation of the kinetically stable pseudorotaxane. Due to its sensitivity towards amine compounds, the activated carbonate end of the encircled thread allowed post‐interlocking aminolysis‐based conversion into mechanically interlocked rotaxanes by providing the same way the carbamate secondary station for the DB24C8 in the thread backbone. Translation of the DB24C8 along the threaded axle between the two molecular stations was investigated.

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Interplay between a Foldamer Helix and a Macrocycle in a Foldarotaxane Architecture

Cited by 16 publications

References 71 publications

[3]Foldarotaxane-mediated synthesis of an improbable [2]rotaxane

[3]Foldarotaxane-mediated synthesis of an improbable [2]rotaxane

Foldaxanes: Rotaxane-like Architectures from Foldamers

Study of [2]‐ and [3]Rotaxanes Obtained by Post‐Synthetic Aminolysis of a Kinetically Stable Carbonate‐Containing Pseudorotaxane

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