Noncovalent Lone Pair⋅⋅⋅(No‐π!)‐Heteroarene Interactions: The Janus‐Faced Hydroxy Group

Pavlakos, Ilias; Arif, Tanzeel; Aliev, Abil E.; Motherwell, William B.; Tizzard, Graham J.; Coles, Simon J.

doi:10.1002/anie.201502103

Cited by 26 publications

(23 citation statements)

References 85 publications

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“…The S⋅⋅⋅arene and S⋅⋅⋅pyrazine interactions differ only slightly in favour of the pyrazine, which stands in sharp contrast to the attractive O⋅⋅⋅pyrazine interaction which is favoured by nearly 6 kJ mol −1 over the O⋅⋅⋅arene counterpart. We have previously measured the strength of this O⋅⋅⋅heteroarene interaction for the hydroxy group and a similar value has also been reported by Gung for the noncovalent interaction of an oxygen atom in a 9‐benzyl triptycene unit with a highly fluorinated arene. The simplest explanation for the overall pattern displayed by the oxygen atom is that it essentially involves electrostatic interactions, whilst the behaviour of the sulfur atom is dominated by its much greater polarisabilty (approximately three times larger than that of oxygen) and the presence of vacant orbitals for further interaction.…”

Section: Figuresupporting

confidence: 76%

“…[a] Based on the accuracy of the NMR J coupling measurements (±0.05 Hz),, the uncertainty in p values is estimated to be within ±0.9 %. Full details of NMR measurements are provided in Supporting Information.…”

Section: Figurementioning

confidence: 99%

“…In the first instance, they serve to confirm the measurements made for the oxathiolanes 1 – 8 and dithioketals 9 and 10 in terms of the dominance of the O⋅⋅⋅heteroarene interaction. The greater number of degrees of conformational freedom in the acyclic ketals allows for the optimal orientation of the oxygen lone pair and the methyl group towards the electron‐deficient pyrazine or quinoxaline ring and an even greater measured preference for the O⋅⋅⋅heteroarene interaction over the O⋅⋅⋅arene interaction. Similar arguments also apply in the case of the acyclic dithioketals 11 and 12 .…”

Section: Figurementioning

confidence: 99%

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Noncovalent Interactions of π Systems with Sulfur: The Atomic Chameleon of Molecular Recognition

et al. 2017

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The relative strength of noncovalent interactions between at hioether sulfur atom and various p systems in designed top pan molecular balances was determined by NMR spectroscopy. Compared to its oxygen counterpart, the sulfur atom displays aremarkable ability to interact with almost equal facility over the entire range of p systems studied, with the simple alkene emerging as the most powerfulpartner.With the exception of the O···heteroarene interaction, all noncovalent interactions of sulfur with p systems are favoured over oxygen.Noncovalent interactions involving aromatic systems, [1] such as p-p stacking [2] or cation-p interactions, [3] and the ability of an arene to act as ahydrogen-bond acceptor [4] are all firmly established as vital control elements in molecular recognition and consequently underpin vast areas of chemistry and molecular biology.More recently,asaconsequence of two virtually simultaneous theoretical studies predicting the strength of the related anion-p interaction, [5] this area has witnessed intense research activity. [6] In parallel, following on from the seminal observation of the attractive lone pair···p interaction in stabilizing the Z-DNAs tructure, [7] this force is also rapidly gaining recognition as anew area of supramolecular chemistry. [8] Detailed quantifiable knowledge of the relative strength of these weak forces is now therefore considered to be essential for the rational design of organocatalysts, [9] new drugs and supramolecular materials,aswell as the understanding of three-dimensional structure and function in biological systems.Thec onformational analysis of designed molecular balances [10] with limited degrees of freedom is ap articularly powerful tool for probing the strength, distance and angular dependence of such interactions,and also allows for exploration of all important solvation phenomena. [11] Whilst an increasing number of studies in recent years have focused on measuring the O···p interaction with electron-deficient arenes and heteroarenes, [12] we were surprised to note that quantifiable comparative information using such balances to probe noncovalent interactions involving as ulfur atom with p systems has been almost entirely neglected. Thev ital role played by sulfur in chemical and biological recognition and in drug development is well-recognized. [13] As summarized in an ongoing series of excellent reviews, [1] theinvestigation of the S···arene interaction is essentially based on extensive database mining of protein crystal structures.I nasignificant contribution by Dougherty and co-workers, [14] the strength of aS···arene interaction in the dopamine D2 receptor has been probed by progressive modulation of the electrostatic surface of the arene through fluorination. To the best of our knowledge,i ns pite of the fact that theoretical chemists continue to be intrigued by the noncovalent interactions of asulfur atom with p systems, [15] no quantitative experimental measurements have been reported for either simple alkenes or heteroarenes.I nt erms of ac...

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Section: Figuresupporting

confidence: 76%

Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

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Noncovalent Interactions of π Systems with Sulfur: The Atomic Chameleon of Molecular Recognition

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“…In a similar fashion, replacement of one of the aromatic rings in the bicyclononane balance by an aromatic heterocycle allowed to compare and rank the interactions of a hydroxyl group with benzene, pyrazine and quinoxaline rings (Figure ) …”

Section: Bicyclononane Balances Of Motherwellmentioning

confidence: 99%

Some Recent Advances in the Design and Use of Molecular Balances for the Experimental Quantification of Intramolecular Noncovalent Interactions of π Systems

Aliev

Motherwell

2019

Chemistry A European J

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Herein, various molecular balances used for comparing the strengths of intramolecular noncovalent interactions are reviewed. Our overview indicates that considerable quantitative insight into the strength of noncovalent interactions can be gained through the careful design of molecular balances. Many exciting opportunities certainly exist for the design of further new balances to quantify and dissect the relative strengths of noncovalent interactions as a function of solvation and the importance of the many factors that contribute to overall molecular recognition. However, even simple model molecules can show a multiplicity of intramolecular noncovalent interactions acting in a combined fashion. It is therefore essential to undertake a detailed computational analysis to identify all possible noncovalent interactions present in a selected molecular balance prior to a quantitative experimental assessment of the strength of a particular noncovalent interaction. It is also argued that the words “torsion” and “molecular balance” seem to have become inextricably linked and, in consequence, even top pan and seesaw balances have been mistakenly referred to in these terms.

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“…Seine Forschungsinteressen umfassen die (physikalische) organische und die Organometallchemie, darunter Zinkcarbenoide, übergangsmetallkatalysierte Reaktionen und die Chemie freier Radikale. Zu seinen neuesten Veröffentlichungen in der Angewandten Chemie gehören eine über nichtkovalente Wechselwirkungen funktioneller Gruppen3a und eine über Wechselwirkungen zwischen freien Elektronenpaaren und Heteroarenen 3b…”

Section: Ausgezeichnet …︁unclassified

Preise 2015 der Société Chimique de France

2015

Angewandte Chemie

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Noncovalent Lone Pair⋅⋅⋅(No‐π!)‐Heteroarene Interactions: The Janus‐Faced Hydroxy Group

Cited by 26 publications

References 85 publications

Noncovalent Interactions of π Systems with Sulfur: The Atomic Chameleon of Molecular Recognition

Noncovalent Interactions of π Systems with Sulfur: The Atomic Chameleon of Molecular Recognition

Some Recent Advances in the Design and Use of Molecular Balances for the Experimental Quantification of Intramolecular Noncovalent Interactions of π Systems

Preise 2015 der Société Chimique de France

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