Peptide [4]Catenane by Folding and Assembly

Sawada, Tomohisa; Yamagami, Motoya; Ohara, Kazuaki; Yamaguchi, Kentaro; Fujita, Makoto

doi:10.1002/ange.201600480

Cited by 28 publications

(29 citation statements)

References 42 publications

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“…In other words, the controlled synthesis of parallel/antiparallel, Type I/Type II, and left‐/right‐handed structures, and their individual characterization have not yet been achieved to date. Here, we control the formation of these structural isomers using the folding‐and‐assembly strategy 12‐20 . To do this, we incorporate pyridyl‐appended residues into the octapeptide sequence of 1 , and induce simultaneous folding and assembly of the two peptide strands into the specific isomers of the ds‐β‐helix through metal coordination (Figure 2).…”

Section: Figurementioning

confidence: 99%

Parallel and antiparallel peptide double β‐helices controlled by metal‐induced folding and assembly

et al. 2021

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Short peptides with sequences of alternating l‐ and d‐residues are known to form antiparallel double β‐helical structures, but their equilibrium structures have not been characterized in detail. Here, we use metal coordination of a simple octapeptide, ‐(l‐Val‐d‐Val)4‐, modified with two coordinating side chains at the (i, j)‐th residues to uncover these elusive structures. When (i, j) = (3, 5), complexation with ZnI2 induces a parallel double β‐helix, which is not commonly seen. In contrast, when (i, j) = (5, 7), a commonly occurring antiparallel double β‐helix (Type I) is formed. Interestingly, complexation of the peptide with (i, j) = (3, 7) gives another antiparallel double β‐helix, the unknown Type II structure, which has an inverted orientation of the two strands. Complexation of a monotopic peptide (i = 3) with trans‐PdCl2 yields a Pd(II)‐linked dimeric bundle of two antiparallel β‐helices. These results demonstrate that metal coordination can induce even as‐yet unrecognized structures in the folding and assembly pathways of short peptides. Key points Structural elucidation of elusive peptide nanostructures Precise structural control of double helical molecules Fusion of peptide folding and metal‐directed self‐assembly

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Section: Figurementioning

confidence: 99%

Parallel and antiparallel peptide double β‐helices controlled by metal‐induced folding and assembly

et al. 2021

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“…, which expresses conditional and unconditional topological chirality, 73 and (iii) Fujita's metallo-[2] catenane [Ag 8 (19) 8 ] 8+ , which contains four crossing points (8 2 1 link) and expresses both conditional and unconditional topological chirality. 74 (C) Biasing of co-conformational stereogenic units using non-covalent interactions: (i) a diastereomeric ion pair based on a helically chiral coconformation of Stoddart's cationic catenane 20 4+ and chiral phosphate anion 21 À75 and (ii) a diastereomeric ion pair based on Credi's coconformationally mechanically planar chiral rotaxane 22 and camphor sulfonate (23) (R = CH2-3-pyrenyl).…”

Section: Chiral Derivatization For the Synthesis Of Mixed Covalently And Mechanically Chiral Moleculesmentioning

confidence: 99%

“…Perhaps the most impressive examples of chiral derivatization in the stereoselective synthesis of mechanically chiral catenanes under thermodynamic control have been reported by Fujita and co-workers 73,74,81,82 beginning in 2016 with the report of a metallo- [4]catenane. 83 Catenane [Ag 12 (18) 12 ] 12+ , formed by the self-assembly of 12 equivalents of short peptide 18 and 12 Ag + cations, crystallized from the reaction mixture over 9 weeks (Figure 4B, ii).…”

Section: Chiral Derivatization For the Synthesis Of Mixed Covalently And Mechanically Chiral Moleculesmentioning

confidence: 99%

“…83 Catenane [Ag 12 (18) 12 ] 12+ , formed by the self-assembly of 12 equivalents of short peptide 18 and 12 Ag + cations, crystallized from the reaction mixture over 9 weeks (Figure 4B, ii). 73 Single-crystal X-ray diffraction (SCXRD) revealed [Ag 12 (18) 12 ] 12+ to be composed of four oriented macrocycles linked together to generate a tetra-interlocked structure that has 12 crossing points and expresses unconditional topological chirality. In addition, the rings themselves are oriented, resulting in conditional topological stereogenic units.…”

Section: Chiral Derivatization For the Synthesis Of Mixed Covalently And Mechanically Chiral Moleculesmentioning

confidence: 99%

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Strategies for the Synthesis of Enantiopure Mechanically Chiral Molecules

Maynard

Goldup

2020

Chem

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Mechanically interlocked molecules, such as rotaxanes and catenanes, are composed of two or more covalent subcomponents threaded through one another such that they cannot be separated without breaking a covalent bond. This arrangement can allow the covalent subcomponents to undergo large-amplitude relative motion, and this property of the mechanical bond has been widely exploited in the design and synthesis of molecular machines. Another less well-known property of the mechanical bond is that it can give rise to chirotopic stereogenic units that do not rely on covalent stereogenic elements. Although the study of such ''mechanically chiral'' molecules is expanding, their synthesis in enantiopure form remains challenging. In this Perspective, we review the strategies available, highlighting key examples along the way, and suggest future areas for development.

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“…23,24 It is less common to construct rings from multiple discrete foldamer subunits, but there are examples: Huc has demonstrated homochiral self-sorting of folded segments within macrocycles, 25 and structurally intricate, foldamer-based coordination complexes have been reported by Sawada and Fujita. 26,27 Recent work from our group [28][29][30] has focused on the self-assembly of foldamer monomers into macrocycles via dynamic covalent chemistry, 31,32 as shown in Figure 1a. In particular, we are interested in how folding affects self-assembly and vice versa: Confinement within a cyclic structure imposes conformational constraints on the foldamer subunits, affecting their geometries; at the same time, the (dynamic) geometric preferences of the foldamer ultimately dictate the size and shape of the product that is obtained.…”

Section: Introductionmentioning

confidence: 99%

Folding-Controlled Assembly of Ortho-Phenylene-Based Macrocycles

Kirinda¹,

Hartley

2020

Preprint

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The self-assembly of foldamers into macrocycles is a simple approach to non-biological higher-order structure. Previous work on the co-assembly of ortho-phenylene foldamers with rod-shaped linkers has shown that folding and self-assembly affect each other; that is, the combination leads to new emergent behavior, such as access to otherwise unfavorable folding states. To this point this relationship has been passive. Here, we demonstrate control of self-assembly by manipulating the foldamers’ conformational energy surfaces. A series of o-phenylene decamers and octamers have been assembled into macrocycles using imine condensation. Product distributions were analyzed by gel-permeation chromatography and molecular geometries extracted from a combination of NMR spectroscopy and computational chemistry. The assembly of o-phenylene decamers functionalized with alkoxy groups or hydrogens gives both [2+2] and [3+3] macrocycles. The mixture results from a subtle balance of entropic and enthalpic effects in these systems: the smaller [2+2] macrocycles are entropically favored but require the oligomer to misfold, whereas a perfectly folded decamer fits well within the larger [3+3] macrocycle that is entropically disfavored. Changing the substituents to fluoro groups, however, shifts assembly quantitatively to the [3+3] macrocycle products, even though the structural changes are well-removed from the functional groups directly participating in bond formation. The electron-withdrawing groups favor folding in these systems by strengthening arene–arene stacking interactions, increasing the enthalpic penalty to misfolding. The architectural changes are substantial even though the chemical perturbation is small: analogous o-phenylene octamers do not fit within macrocycles when perfectly folded, and quantitatively misfold to give small macrocycles regardless of substitution. Taken together, these results represent both a high level of structural control in structurally complex foldamer systems and the demonstration of large-amplitude structural changes as a consequence of a small structural effects.

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Peptide [4]Catenane by Folding and Assembly

Cited by 28 publications

References 42 publications

Parallel and antiparallel peptide double β‐helices controlled by metal‐induced folding and assembly

Parallel and antiparallel peptide double β‐helices controlled by metal‐induced folding and assembly

Strategies for the Synthesis of Enantiopure Mechanically Chiral Molecules

Folding-Controlled Assembly of Ortho-Phenylene-Based Macrocycles

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