Interaction of heterocyclic thiols/thiones eliminated from cephalosporins with iodine and its biological implications

Tamilselvi, A.; Mugesh, Govindasamy

doi:10.1016/j.bmcl.2010.04.087

Cited by 40 publications

(24 citation statements)

References 36 publications

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“…This example will be discussed in more detail in the section on halogen bonds involving metal complexes. Four structures containing linear I–I ··· S interactions accepted by thiones24b were also found in the CSD. Three structures with five‐membered heterocycles (WURGEW, WURGIA and WURGOG) were reported in which the I–I bond lengths are significantly elongated (I–I 2.88–3.03 Å), whereas the distance in the fourth structure with a six‐membered heterocycle (WURHAT) is closer to the normal value (I–I 2.76 Å).…”

Section: Halogen Bonding With Organic Molecules In the Solid Statementioning

confidence: 90%

“…In these cases, the I 2 is located between two N acceptors, generating a polymeric chain of linear N ··· I–I ··· N assemblies (Figure 2, a). Nevertheless, the I ··· N interaction is much weaker in these systems according to the contact distances (IHISEY: 2.99 Å;24a WURGAS: 2.94 Å;24b corresponding to 15 and 17 % reduction, respectively). The size and shape of the acceptor molecule as well as the crystal‐packing effects have been shown to be very important for the stability of the N ··· I–I ··· N assembly 24…”

Section: Halogen Bonding With Organic Molecules In the Solid Statementioning

confidence: 92%

“…The I ··· S distances for the five‐membered heterocyclic derivatives are 2.55 (WURGEW, 33 % reduction), 2.62 (WURGIA, 31 % reduction) and 2.68 Å (WURGOG, 29 % reduction), whereas for the complex WURHAT, an I ··· S distance of 3.13 Å (only 17 % reduction) was observed. In the latter case, the S ··· I–I ··· S‐type motif was observed, which explains the longer I ··· D distance 24b…”

Section: Halogen Bonding With Organic Molecules In the Solid Statementioning

confidence: 94%

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Alternative Motifs for Halogen Bonding

et al. 2013

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The halogen‐bonding interaction is one of the rising stars in supramolecular chemistry. Although other weak interactions and their influence on the structure and chemistry of various molecules, complexes and materials have been investigated thoroughly, the field of halogen bonding is still quite unexplored and its impact on chemistry in general is yet to be fully revealed. In principle, every Y–X bond (Y = electron‐withdrawing atom or moiety, X = halogen atom) can act as a halogen‐bond donor when the halogen is polarized enough by Y. Perfluorohalocarbons are iconic halogen‐bond donor molecules in which Y is a perfluorinated aryl or alkyl moiety and X is either iodine or bromine. In this article, alternative halogen‐bond motifs such as X2···A and Ar–X···A [A = Lewis basic halogen‐bond‐accepting atom of a molecule or ion; Ar = neutral or charged (hetero)aromatic system] are reviewed. In addition, haloalkenes, haloalkynes, N‐haloamides and other non‐metallic halogen‐bond donors and their respective halogen‐bonded structures will also be described. Although purely organic halogen‐bonding motifs are very prominent, the role of metal complexes in halogen bonding is becoming increasingly evident as well, which is also reflected in this review. Finally, halogen bonding in solution is briefly highlighted. Contemporary research is proving that halogen bonding is more than a solid‐state phenomenon and is now a well‐recognized weak interaction in chemistry.

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Section: Halogen Bonding With Organic Molecules In the Solid Statementioning

confidence: 90%

Section: Halogen Bonding With Organic Molecules In the Solid Statementioning

confidence: 92%

Section: Halogen Bonding With Organic Molecules In the Solid Statementioning

confidence: 94%

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Alternative Motifs for Halogen Bonding

et al. 2013

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“…the PTP is a neutral zwitterionic molecule, it is possible to avoid introducing any undesirable cations into the system. I2 is the simplest bidentate XB donor, which can be used to link organic molecules together via XB [35][36][37][38][39][40]. However, I2 is not always the most ideal linker due to its redox properties, which easily lead to unwanted side reactions.…”

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confidence: 99%

A Novel Halogen Bond Acceptor: 1-(4-Pyridyl)-4-Thiopyridine (PTP) Zwitterion

2020

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Sulfur is a widely used halogen bond (XB) acceptor, but only a limited number of neutral XB acceptors with bifurcated sp3-S sites have been reported. In this work a new bidentate XB acceptor, 1-(4-pyridyl)-4-thiopyridine (PTP), which combines sp3-S and sp2-N acceptor sites, is introduced. Three halogen bonded cocrystals were obtained by using 1,4-diiodobenzene (DIB), 1,4-diiodotetrafluorobenzene (DIFB), and iodopentafluorobenzene (IPFB) as XB donors and PTP as acceptor. The structures of the cocrystals showed some XB selectivity between the S and N donors in PTP. However, the limited contribution of XB to the overall molecular packing in these three cocrystals and the results from DSC measurements clearly point out the synergetic influence and interplay of all noncovalent interactions in crystal packing of these compounds.

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“…Thiocarbonyl compounds are fascinating molecules with wide range of biological activities . Tautomerization in thiocarbonyl systems, in particular, has been found to be one of the significant steps in certain enzymatic reactions and in many physiological processes . The studies that detail the importance of thione moiety in antithyroid agents and the effect of thione–thiol tautomerism on peroxidase‐catalysed oxidation reactions and 4′‐phosphopantothenoylcysteine decarboxylase (PPC‐DC) catalyzed decarboxylation reaction were reported .…”

Section: Introductionmentioning

confidence: 99%

Density functional evaluation and a feasibility study of intramolecular thione-thiol tautomerization

Jayasree

Sreedevi

2017

Int J Quantum Chem

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Performance of various density functionals for use in geometry and energetics calculation of thiocarbonyl systems is evaluated. The three biologically significant systems such as 2-methyl-3-thiosemicarbazide, 1-acetyl-2-thiohydantoin and bornane-2-thione are selected for the geometry analysis. Energy of tautomerization of thioacetone and enthalpy of formation of 2thiohydantoin are considered for analyzing the performance in energetics. Minnesota functionals such as M05-2X, M06-2X and range separated hybrid functional wB97 give best results in both geometry and energetics calculations. Studies on basis set effect showed reliable performance by 6-31 1 G* and 6-3111G** over higher basis sets. Feasibility of tautomerization in the aforementioned thiones has been investigated using the best performing density functionals.The proposed thione-thiol tautomerization step during PPC-DC catalyzed decarboxylation reaction has also been investigated and the computed high energy barrier shows less feasibility of the reaction. K E Y W O R D S basis set effect, calibration, density functionals, tautomerization, thiocarbonyl systems 1 | I N T R O D U C T I O NThiocarbonyl compounds are fascinating molecules with wide range of biological activities. [1][2][3] Tautomerization in thiocarbonyl systems, in particular, has been found to be one of the significant steps in certain enzymatic reactions and in many physiological processes. [4][5][6][7][8] The studies that detail the importance of thione moiety in antithyroid agents and the effect of thione-thiol tautomerism on peroxidasecatalysed oxidation reactions and 4 0 -phosphopantothenoylcysteine decarboxylase (PPC-DC) catalyzed decarboxylation reaction were reported. [7,8] There were reports that also show the tautomerization of thiobases such as thiouracil and thiocytosine which are the constituents of t-RNA species. [4] The significance of thione-thiol tautomerism in these physiological processes demands a detailed study of its energetics. [9,10] Density functional theory (DFT) has become a powerful and time effective method for the calculation of electronic structure and other molecular properties nowadays. [11][12][13][14][15][16] Wide application of DFT methods evinces its unparallel impact on quantum mechanics to solve challenging problems in chemistry. Various DFT methods differ in their exchange-correlation functionals and this difference makes the best functional for one application often not the best for the other. [17] Therefore, the selection of a density functional from a plethora of reported exchange correlation functionals for a particular chemical problem becomes essential. Several such calibration studies have been reported. [18][19][20][21][22][23][24][25][26] Methods such as BP86 and B3LYP were found to perform well for the analysis of intermediate and transition state structures and the relative energy calculations of chemical processes. [21] However, our initial studies using B3LYP/6-31 1 G* produced a contradictory result for the geometry of simple carbonyl sys...

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Interaction of heterocyclic thiols/thiones eliminated from cephalosporins with iodine and its biological implications

Cited by 40 publications

References 36 publications

Alternative Motifs for Halogen Bonding

Alternative Motifs for Halogen Bonding

A Novel Halogen Bond Acceptor: 1-(4-Pyridyl)-4-Thiopyridine (PTP) Zwitterion

Density functional evaluation and a feasibility study of intramolecular thione-thiol tautomerization

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