Assembly-driven synthesis of hybrid molecular capsules controlled by chiral sorting

Wierzbicki, Michał; Szumna, Agnieszka

doi:10.1039/c3cc41515e

Cited by 16 publications

(14 citation statements)

References 24 publications

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“…Chiral self‐sorting has been observed in reactions under thermodynamic control (covalent condensation[4c], and coupling reactions,[3e] metal complexation,[30c], hydrogen bonding, etc.) leading, from a racemic mixture of chiral precursors, either to the preferred formation of chiral n ‐mers composed of homochiral components or to an achiral meso species .…”

Section: Resultsmentioning

confidence: 99%

Generation of Cryptophanes in Water by Disulfide Bridge Formation

Brégier¹,

Hudeček

Chaux³

et al. 2017

Eur J Org Chem

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International audienceCryptophanes are receptors consisting of two bridging concave cyclotribenzylene (CTB) subunits. The formation of cryptophanes in basic aqueous solutions (0.1 M MOD; M = Li, Na, K, and Cs) by disulfide bridge formation has been investigated. Two original CTBs, 1H(6) and 2H(6), derived from cyclotriphenolene through the introduction of mercaptomethyl and mercapto substituents, respectively, were synthesized. Cryptophane formation by slow oxygenation of 1(6-) was observed only in the presence of Me4N+ as template, which yielded the diastereomeric forms in a ratio of around 82:18. By contrast, the rigid CTB 2H(6) yielded a cryptophane stereoselectively without a template. Interestingly, air oxidation of a 1:1 mixture of 1(6-) and 2(6-) in the presence of Me4N+ (0.5-1 equiv./1(6-)) in 0.1 m LiOD led to the exclusive formation of the cryptophane complex [(1.1)(6-)superset of+NMe4], (2.2)(6-) being formed only in very minor amounts. No mixed species were detected in the reaction mixtures. The stabilities of the diastereomers of the protonated cryptophanes were calculated in the gas phase by DFT at the omega B97XD 6-311G(d,p) level of theory

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Section: Resultsmentioning

confidence: 99%

Generation of Cryptophanes in Water by Disulfide Bridge Formation

Brégier¹,

Hudeček

Chaux³

et al. 2017

Eur J Org Chem

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“…We previously appliedasimilar assembly-based approach to the synthesis of heterochiralc apsules that cannot be obtained by standarda pproaches. [24] In our view,t hese examples support the crucial role of templation followed by self-assembly in the synthesis of complex molecules.…”

Section: Templated Synthesis Of Cavitandsmentioning

confidence: 53%

Self‐Assembly and Ordering of Peptide‐Based Cavitands in Water and DMSO: The Power of Hydrophobic Effects Combined with Neutral Hydrogen Bonds

Eichstaedt

Szpotkowski

Grajda

et al. 2019

Chemistry A European J

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Directional self-assembly of uncharged molecules in water is am ajor challenge in supramolecular chemistry. Herein,i ti sdemonstrated that peptide-based cavitands wrap around ah ydrophobic core (fullerene C 60 )b yacombination of the hydrophobic effect and hydrogen-bonding interactions to form highly ordered three-componentc omplexes in water that resemblet he molten-globule stage of proteinf olding. The complexesw ere characterized by DOSY NMR spectroscopy,s mall-angleX -ray scattering, andc ircular dichroism, and their structuresw ere confirmed by X-ray crystallography.E nhancemento ft he CD signalsb yn early one order of magnitude and increased hydrolytic stability of hydrazone bonds of the complexes relative to the nonassembled species were observed.I nc ontrast, DMSO and DMSO/ waterm ixtures were found to be highly disintegrative for these complexes. Interestingly,s ome cavitands cano nly be synthesized in the presence of the hydrophobic template followed by disassemblyoft he complexes.[a] Dr.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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“…Compound 1 was synthesized as previously reported. 19 A 10 mg sample of 1 was crystallized from acetone. The crystals were quite large but decomposed within seconds after removal from the mother liquid.…”

Section: Methodsmentioning

confidence: 99%

Experiences with applications of macromolecular tools in supramolecular crystallography

Wierzbicki¹,

Gilski²,

Jaskólski³

et al. 2014

CrystEngComm

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Supramolecular structures, with ever increasing size ranging from a few up to tens of nanometres, represent an intermediate stage between small molecules and biological macromolecules. Many crystal structures of these large supramolecular assemblies have been solved using dual space algorithms. However, supramolecular assemblies with a capsular shape present a particular challenge for crystallography, especially when they are chiral and composed of only light atoms. In this paper, we show that the application of "routine" macromolecular tools may be of great help in solving the crystal structures of supramolecular assemblies that are otherwise refractory to the routine methods of small molecule crystallography. Specifically, we have applied the method of molecular replacement as implemented in PHASER in order to solve the crystal structure of a chiral organic capsule, which could not be determined using direct or dual space methods. By utilizing various models consisting of welldefined supramolecular "bricks" or modelled structures, we show how model size (fraction of the asymmetric unit) and quality (root mean square deviation from target) influence the success rate of medium sized non-protein structures. The results indicate that supramolecular structures, that are still "small molecules" for macromolecular standards, can be successfully solved using even very small models, down to 25% by weight of the contents of the asymmetric unit.

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Assembly-driven synthesis of hybrid molecular capsules controlled by chiral sorting

Cited by 16 publications

References 24 publications

Generation of Cryptophanes in Water by Disulfide Bridge Formation

Generation of Cryptophanes in Water by Disulfide Bridge Formation

Self‐Assembly and Ordering of Peptide‐Based Cavitands in Water and DMSO: The Power of Hydrophobic Effects Combined with Neutral Hydrogen Bonds

Experiences with applications of macromolecular tools in supramolecular crystallography

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