Intramolecular Hydrogen Bonds Preorganize an Aryl-triazole Receptor into a Crescent for Chloride Binding

Lee, Semin; Hua, Yilei; Park, Hyunsoo; Flood, Amar H.

doi:10.1021/ol1005856

Cited by 127 publications

(87 citation statements)

References 44 publications

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“…This reaction has found use in medicinal chemistry, [5] biology, [6] material science, [7] anion binding, [8][9][10] and sensing studies [11] as well as in building ligands for coordination and organometallic chemistry. [12][13][14][15][16][17][18][19][20][21][22][23][24] After the initial discovery of the use of tris[(1-benzyl-1H-1,2,3-triazole-4-yl)methyl]amine (tbta) as an additional component of the catalytic mixture, which leads to acceleration of reactions and improvement of yields, [25] efforts have been made to use other such ligands for improving this method.…”

Section: Introductionmentioning

confidence: 99%

Copper(I) Complexes of Normal and Abnormal Carbenes and Their Use as Catalysts for the Huisgen [3+2] Cycloaddition between Azides and Alkynes

2011

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Complexes of general formula [(NHC)Cu(μ-I) 2 Cu(NHC)] (NHC = 1-benzyl-3-butylbenzimidazolin-2-ylidene for 7; NHC = 1-benzyl-3-isopropylbenzimidazolin-2-ylidene for 8 NHC = 1-butyl-3-isopropylbenzimidazolin-2-ylidene for 9) and [(aNHC)CuI] {aNHC = 1-benzyl-3-methyl-4-phenyl-1H-1,2,3-triazol-3-ium-5-ylidene for 10; 3-methyl-1-[2-(methylthio)phenyl]-4-phenyl-1H-1,2,3-triazol-3-ium-5-ylidene for 11} were synthesized from CuI and the corresponding azolium salts. All complexes were fully characterized by spectroscopic methods, and single-crystal X-ray structural analyses were performed for 7 and 11. Complex 7 exhibits an iodidobridged dicopper(I) form in the solid state. The copper centers in 7 adopt a trigonal coordination. The intramolecular Cu-Cu distance is 2.896(2) Å. In contrast to 7, 11 is mononuclear, and the copper center has a linear coordination. All the complexes were tested for their efficiency as catalysts in the [3+2] cycloaddition reaction between azides and alkynes.

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Section: Introductionmentioning

confidence: 99%

Copper(I) Complexes of Normal and Abnormal Carbenes and Their Use as Catalysts for the Huisgen [3+2] Cycloaddition between Azides and Alkynes

2011

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“…4-( t -Butyl)phenyl azide has previously been synthesized by diazotization of 4- t -butylaniline. 37 …”

Section: Methodsmentioning

confidence: 99%

Synthesis of Deuterated 1,2,3-Triazoles

Akula

Lakshman

2012

J. Org. Chem.

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The copper-catalyzed azide–alkyne cycloaddition (CuAAC) is a highly effective method for the selective incorporation of deuterium atom into the C-5 position of the 1,2,3-triazole structure. Reactions of alkynes and azides can be conveniently carried out in a biphasic medium of CH2Cl2/D2O, using the CuSO4/Na ascorbate system. The mildness of the method renders it applicable to substrates of relatively high complexity, such as nucleosides. Good yields and high levels of deuterium incorporation were observed. A reaction conducted in equimolar H2O and D2O showed 2.7 times greater incorporation of hydrogen atom as compared to deuterium. This is consistent with the H+ and D+ ion concentrations in H2O and D2O, respectively. With appropriately deuterated precursors, partially to fully deuterated triazoles were assembled where the final deuterium atom was incorporated in the triazole-forming step.

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“…51 Aryl-triazoles are effective 52-54 ion-binding motifs with straightforward 55,56 and efficient synthesis protocols and they have been shown in solution-based supramolecular systems to act as interlocked molecules, 57 chelators, 58 and sensors. [59][60][61] The particular aryl-triazole motif employed in this study ( Figure 2) has been previously explored in the solution phase 48,62 for its propensity to sequester anions from organic solvents. This property is the direct result of the electropositive pocket, which is strongly polarized by the triazoles (red in Figure 2) and amide moieties.…”

Section: Molecular Designmentioning

confidence: 99%

Living on the edge: Tuning supramolecular interactions to design two-dimensional organic crystals near the boundary of two stable structural phases

Hirsch

McDonald

Flood

et al. 2015

The Journal of Chemical Physics

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One of the benefits of supramolecular assemblies that form at dynamic interfaces is the opportunity to develop condensed phase systems that respond to environmental stimuli. A prerequisite of this responsive behavior is that the supramolecular system be designed to sit very near the stability of two or more crystal structures. We have created such a bi-phasic system with aryl-triazole oligomers by investigating how phase morphology is controlled by the interplay between interactions that involve the oligomer's dipolar cores (Δμ = 3.5 debye), van der Waals contacts of their pendant alkyl chains (C4-C18), and close-contact hydrogen bonding. Scanning tunneling microscopy experiments conducted at the solution-graphite interface allow sub-molecular resolution of the ordered monolayers to unambiguously determine the packing and structure of two principle phases, α and β. The system is balanced very near the edge of phase stability, evidenced by co-existent phases present over short time frames and by the changes in preference between the two 2D supramolecular assemblies that occur with small modifications to the molecular structure. We demonstrate that the bi-phasic behavior can be understood as a balance between electrostatic interactions and van der Waals contacts, two variables within a larger parameter space, allowing synthetic design to move this solution-surface system across the stability boundary of different condensed-phase structures. These findings are a foundation for the development of environmentally responsive 2D supramolecular arrays.

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Intramolecular Hydrogen Bonds Preorganize an Aryl-triazole Receptor into a Crescent for Chloride Binding

Abstract: Aryl-triazole pentads have been preorganized with intramolecular hydrogen bonds to enhance chloride binding. This outcome highlights the dual hydrogen bond donor and acceptor properties of 1,2,3-triazoles.

Cited by 127 publications

References 44 publications

Copper(I) Complexes of Normal and Abnormal Carbenes and Their Use as Catalysts for the Huisgen [3+2] Cycloaddition between Azides and Alkynes

Copper(I) Complexes of Normal and Abnormal Carbenes and Their Use as Catalysts for the Huisgen [3+2] Cycloaddition between Azides and Alkynes

Synthesis of Deuterated 1,2,3-Triazoles

Living on the edge: Tuning supramolecular interactions to design two-dimensional organic crystals near the boundary of two stable structural phases

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