Absolute structure determination of compounds with axial and planar chirality using the crystalline sponge method

Yoshioka, Shin; Inokuma, Yasuhide; Hoshino, Manabu; Sato, Takashi; Fujita, Makoto

doi:10.1039/c5sc01681a

Cited by 107 publications

(77 citation statements)

References 25 publications

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“…26,27 Inclusion complexes have recently become focus of attention to study the incorporated molecules, either in an unusual conformation, 28 or to obtain structural information of a hard to crystallise compound. 29,30 Considering the variation in size and interaction potential in bio-isosteric groups, the choice of replacement group will influence the crystal structure of the substances, as has recently been shown for a series of trityl compounds. 31 In addition, change of halogen substituents from chloro via bromo to iodo on phloroglucinol has been shown to influence the incorporation mode of water into the crystal structure.…”

Section: Introductionmentioning

confidence: 99%

Influence of Bio-Isosteric Replacement on the Formation of Templating Methanol and Acetonitrile Solvates in Lophines

Kitchen

Melvin

Najib

et al. 2016

Crystal Growth & Design

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Bio-isosteric replacement is a frequently used tool in medicinal chemistry. While the pharmacological activity is not influenced by the exchange of substituents, the solid-state characteristics and formation of different crystal forms may well be altered dramatically, jeopardizing the processability and safety of the drug compound. In this study we investigate a series of triphenylimidazole (TPI) derivatives as model compounds with the bio-isosteric exchange of only one halogen position (F, Cl, Br, I). Crystallization from two industrially used solvents (methanol and acetonitrile) reveals solvate formation of all TPIs, for which the basic hydrogen bonded motif does not change. The three-dimensional packing depends on the size of the substituent and changes from fluoroto chloro-and bromo-substitution but remains the same for the larger iodo-substituent. From acetonitrile, only F-TPI and Cl-TPI form an isomorphic channel solvate, which in both cases desolvates reversibly to an isomorphic crystal form. Due to the halogen atom lining of the channels, bromine and iodine are too large to generate a stable packing. This study illustrates the importance of understanding the influence of bio-isosteric substitution on the solid state, in order to best utilize this common tool.

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Section: Introductionmentioning

confidence: 99%

Influence of Bio-Isosteric Replacement on the Formation of Templating Methanol and Acetonitrile Solvates in Lophines

Kitchen

Melvin

Najib

et al. 2016

Crystal Growth & Design

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“…However, the potential to inspect unstable moieties or molecules that are not easily crystallised in pure form is highly attractive, and a range of targets has been recently investigated to further demonstrate the utility of the strategy. [54][55][56][57][58][59][60][61] The characterised guest molecules range from simple molecules 54 to reactive acrylate esters 56 and complex Please do not adjust margins Please do not adjust margins molecules with axial and planar chirality, 58 (1R)-(-)-menthyl acetate, 59 α-humulene and its oxidized subproducts. 60 The 'crystalline sponge' approach has also been developed for porous organic materials 61 mirroring studies in MOFs.…”

Section: Mof As Crystallisation Matricesmentioning

confidence: 99%

Emerging applications of metal–organic frameworks

et al. 2016

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Metal-organic Frameworks are a unique class of materials well known for their crystallinity and ultra-high porosity. Since their first report over fifteen years ago, research in this area has sought to actively exploit these properties, especially in gas adsorption. In this article we canvass some emerging topics in the field of MOF research that show promise for new applications in areas such as biotechnology, catalysis, and microelectronics. 26 and Cytochrome c 27 into Tb-based MOFs. These examples were limited to biomacromolecules with sizes smaller than the MOF cavities, although more recent work by Yaghi and coworkers 28has demonstrated the precise tuning of the pore size to adsorb and accommodate bigger biomacromolecules, such as myoglobin and green fluorescent protein.

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“…The capacity of porous coordination networks to order guest species within their pores has previously been refined and exploited by Inokuma et al [33][34][35], among others [36][37][38], to facilitate X-ray crystallographic characterization of large guest molecules without the need for direct crystallization of the target compound. In 1·Co-ACN (a derivative of 1·Co prepared in acetonitrile rather than ethanol) and 1·Cu, the frameworkanchored coordinating sites and a confined pore environment combine to encourage the ordering of additional discrete metal complexes in the MOF pores, as described below.…”

Section: Non-framework-bound Complexes Within Mofmentioning

confidence: 99%

X-ray crystallographic insights into post-synthetic metalation products in a metal–organic framework

Huxley

Coghlan

Bloch

et al. 2017

Phil. Trans. R. Soc. A.

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ResearchCite this article: Huxley MT, Coghlan CJ, Bloch WM, Burgun A, Doonan CJ, Sumby CJ. 2017 X-ray crystallographic insights into post-synthetic metalation products in a metal-organic framework. Post-synthetic modification of metal-organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the postsynthetic incorporation of transition-metal complexes within MOFs, a process known as 'metalation', is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1, contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1 prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1 with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray

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Absolute structure determination of compounds with axial and planar chirality using the crystalline sponge method

Abstract: The absolute structure determination of compounds with axial and planar chirality obtained by recently developed asymmetric syntheses was achieved using the crystalline sponge method without using any reference compounds or synthetic modifications.

Cited by 107 publications

References 25 publications

Influence of Bio-Isosteric Replacement on the Formation of Templating Methanol and Acetonitrile Solvates in Lophines

Influence of Bio-Isosteric Replacement on the Formation of Templating Methanol and Acetonitrile Solvates in Lophines

Emerging applications of metal–organic frameworks

X-ray crystallographic insights into post-synthetic metalation products in a metal–organic framework

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