The Importance of Length and Flexibility of Macrocycle‐Containing Molecular Translocators for the Synthesis of Improbable [2]Rotaxanes

Riss‐Yaw, Benjamin; Clavel, Caroline; Laurent, Philippe; Waelès, Philip; Coutrot, Frédéric

doi:10.1002/chem.201802831

Cited by 20 publications

(10 citation statements)

References 42 publications

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“…Artificial molecular machines that can perform tasks in chemical synthesis [12][13][14][15][16][17][18][19][20][39][40][41][42][43][44][45] strain the limits of rational design 46 given current levels of understanding of chemistry. For a molecular machine to build a new class of sequence polymer, the machine must use building blocks that are sufficiently robust, both initially and as intermediates, for them to be stable while attached to the track (in this case not undergoing side reactions for up to 5 days under the reaction conditions used for machine operation) but sufficiently reactive to be abstracted by the machine-tethered chain.…”

Section: Discussionmentioning

confidence: 99%

A Track-Based Molecular Synthesizer that Builds a Single-Sequence Oligomer through Iterative Carbon-Carbon Bond Formation

McTernan

Leigh

2020

Chem

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Molecular machines, such as ribosomes, are ubiquitous in biology. These natural systems are inspiring artificial systems that move along tracks, picking off and joining building blocks in sequence. To date, such small-molecule machines have used amide formation to connect building blocks, much like the ribosome. Here, the design, synthesis, and operation of a track-based molecular machine that iteratively forms a continuous backbone of carbon-carbon bonds is described. This new class of de novo molecular synthesizer utilizes chemistry and reactivity patterns unavailable to biological machines.

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Section: Discussionmentioning

confidence: 99%

A Track-Based Molecular Synthesizer that Builds a Single-Sequence Oligomer through Iterative Carbon-Carbon Bond Formation

McTernan

Leigh

2020

Chem

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“…Beyond the synthesis of a new pH‐sensitive Weinreb amide‐containing molecular shuttle, we envisaged the cleavage of the encircled axle of 7 by a Grignard reagent (Scheme ). Post‐interlocking modification of such amide‐containing rotaxanes could be of interest for the synthesis of challenging rotaxanes such as those that do not contain any efficient template site . Indeed, this chemical route, which would use the methoxyamine 4 as a translocator, of DB24C8, would allow the access to rotaxanes that consists of an encircled ketone‐containing axle, nay a hydrocarbon axle after subsequent reduction of the ketone moiety to a methylene unit.…”

Section: Resultsmentioning

confidence: 99%

Weinreb Amide as Secondary Station for the Dibenzo‐24‐crown‐8 in a Molecular Shuttle

Gauthier

Coutrot

2019

Eur J Org Chem

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Here is reported the synthesis of a new molecular shuttle: it consists of a dibenzo‐24‐crown‐8 (DB24C8) that surrounds a molecular axle containing an ammonium group and a newly considered Weinreb amide as stations. At the protonated state the DB24C8 is localized around the best ammonium station, while deprotonation‐carbamoylation of the ammonium triggers the shuttling of the macrocycle around the Weinreb amide site. Further post‐interlocking modification of the [2]rotaxane was attempted through the cleavage of the Weinreb amide bond using a Grignard reagent. While the non‐interlocked molecular axle was cleaved after a short time in mild conditions, the Weinreb amide bond remained unaltered in the [2]rotaxane species over time, even in the presence of a larger amount of Grignard and at a higher temperature, highlighting the protection shield of the macrocycle around the encircled axle.

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“…Rotaxane-based artificial molecular machines have previously been developed that produce short sequence-specific oligomers, most commonly peptides, in an approach inspired by aspects of the way the ribosome builds proteins. − However, a significant limitation of current track-based molecular synthesizers is that when each amino acid is extracted from the strand, the resulting cyclic transition state that transfers the amino acid to the terminus of the growing chain increases in size . Every addition slows the transfer of further amino acids until eventually other processes (intermolecular reactions, hydrolysis, etc.)…”

Section: Introductionmentioning

confidence: 99%

Sequence-Selective Decapeptide Synthesis by the Parallel Operation of Two Artificial Molecular Machines

et al. 2021

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We report on the preparation of a decapeptide through the parallel operation of two rotaxane-based molecular machines. The synthesis proceeds in four stages: (1) simultaneous operation of two molecular peptide synthesizers in the same reaction vessel; (2) selective residue activation of short-oligomer intermediates; (3) ligation; (4) product release. Key features of the machine design include the following: (a) selective transformation of a thioproline building block to a cysteine (once it has been incorporated into a hexapeptide intermediate by one molecular machine); (b) a macrocycle-peptide hydrazine linkage (as part of the second machine) to differentiate the intermediates and enable their directional ligation; and (c) incorporation of a Glu residue in the assembly module of one machine to enable release of the final product while simultaneously removing part of the assembly machinery from the product. The two molecular machines participate in the synthesis of a product that is beyond the capability of individual small-molecule machines, in a manner reminiscent of the ligation and post-translational modification of proteins in biology.

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The Importance of Length and Flexibility of Macrocycle‐Containing Molecular Translocators for the Synthesis of Improbable [2]Rotaxanes

Cited by 20 publications

References 42 publications

A Track-Based Molecular Synthesizer that Builds a Single-Sequence Oligomer through Iterative Carbon-Carbon Bond Formation

A Track-Based Molecular Synthesizer that Builds a Single-Sequence Oligomer through Iterative Carbon-Carbon Bond Formation

Weinreb Amide as Secondary Station for the Dibenzo‐24‐crown‐8 in a Molecular Shuttle

Sequence-Selective Decapeptide Synthesis by the Parallel Operation of Two Artificial Molecular Machines

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