The active template approach to interlocked molecules

Denis, Mathieu; Goldup, Stephen M.

doi:10.1038/s41570-017-0061

Cited by 239 publications

(135 citation statements)

References 72 publications

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“…A critical breakthrough in accessing enantiopure mechanically chiral rotaxanes was achieved in the elegant work of Bordoli and Goldup (Figure ) . Using a CuAAC “click”‐active metal template synthesis, they constructed rotaxane 24 from directional macrocycle 21 and two half threads—achiral alkyne 22 and the other enantiopure azide 23 . The diastereomers of 24 were formed in an essentially 1:1 ratio, but crucially they could be separated by standard flash chromatography.…”

Section: Chirality Arising As a Consequence Of The Mechanical Bondmentioning

confidence: 99%

Chiral Catenanes and Rotaxanes: Fundamentals and Emerging Applications

Evans

2017

Chemistry A European J

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Molecular chirality provides a key challenge in host–guest recognition and other related chemical applications such as asymmetric catalysis. For a molecule to act as an efficient enantioselective receptor, it requires multi‐point interactions between host and chiral guest, which may be achieved by an appropriate chiral 3D scaffold. As a consequence of their interlocked structure, catenanes and rotaxanes may present such a 3D scaffold, and can be chiral by inclusion of a classical chiral element and/or as a consequence of the mechanical bond. This Minireview presents illustrative examples of chiral [2]catenanes and [2]rotaxanes, and discusses where these molecules have been used in chemical applications such as chiral host–guest recognition and asymmetric catalysis.

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Section: Chirality Arising As a Consequence Of The Mechanical Bondmentioning

confidence: 99%

Chiral Catenanes and Rotaxanes: Fundamentals and Emerging Applications

Evans

2017

Chemistry A European J

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“…The search for new rotaxanes during the last 50 years has resulted in many studies describing different synthetic routes, dynamic movements in solution, mechanical bonds,, and consequent properties of these kinds of molecules,, which has generated a large set of new molecules with interesting characteristics. With this, it is possible to observe that rotaxane studies are mainly focused on two main fronts: the synthesis and obtaining of these molecules, and the study of their movement and properties.…”

Section: Introductionmentioning

confidence: 99%

Crystallization Mechanisms Applied to Understand the Crystal Formation of Rotaxanes

et al. 2019

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The present study discusses the crystalline packing formation of several [2]rotaxanes with Leigh‐type tetralactam macrocycle bearing different threads. The presence of solvent molecules in some structures are also addressed to shed some light on this matter. Additionally, the degree of similarity between supramolecular structures of rotaxanes was discussed using similarity indices. For this, new descriptors and crystallization mechanisms, which were proposed in terms of contact area and stabilization energy, were carried out to evaluate the rotaxane molecules. It was possible to observe similar general stages of crystallization dominated by the formation of 1D‐blocks and, in fewer cases, by dimers in the first stage of nucleation. The preference for the formation of 1D nuclei resides in the large contact area and complementarity involved in the large set of interactions between the rotaxanes at the earliest stages of crystallization. In this context, it was possible to propose when solvent molecules are trapped between the rotaxanes during crystal formation. Therefore, a unique example of a rotaxane whose topology favored the entrapment of water molecules between rotaxanes during the first stage of the crystallization process is presented. Crystallization mechanisms showed to be a valuable asset in the supramolecular investigation of rotaxanes in the crystalline state.

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“…The target [2]rotaxanes were synthesized by the active metal templation (AMT) protocol, where endotopic coordination of the catalytically‐active metal cation within the cavity of a macrocycle forms a covalent bond between axle precursors through the cavity of the macrocycle , . The retrosynthetic strategy towards the target monocationic rotaxane is shown in Scheme A.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Bromide Sensing with a Halogen Bonding [2]Rotaxane

Lim

Beer

2018

Eur J Org Chem

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The selective electrochemical sensing of heavy halides, such as bromide, over more charge‐dense counterparts, like chloride, using mechanically‐interlocked structures remains a formidable challenge. Using the active‐metal templation methodology, the first redox‐active ferrocene‐appended rotaxane containing an all‐halogen bonding anion binding cavity was synthesised. 1H NMR binding studies in aqueous–organic solvent media demonstrated a marked recognition bias for heavy halides, facilitating the selective redox sensing of bromide over chloride to be demonstrated for the very first time with an interlocked host molecule.

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The active template approach to interlocked molecules

Cited by 239 publications

References 72 publications

Chiral Catenanes and Rotaxanes: Fundamentals and Emerging Applications

Chiral Catenanes and Rotaxanes: Fundamentals and Emerging Applications

Crystallization Mechanisms Applied to Understand the Crystal Formation of Rotaxanes

Electrochemical Bromide Sensing with a Halogen Bonding [2]Rotaxane

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