Syntheses and redox behavior of novel cyclic hosts having multiple redox centers of NAD+ analogue

Kuroda, Yasuhisa; Seshimo, Hidenori; Kondo, Toshio; Shiba, M.; Ogoshi, Hisanobu

doi:10.1016/s0040-4039(97)00784-3

Cited by 10 publications

(12 citation statements)

References 8 publications

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“…Herein is described the successful preparation of 4 , which represents the first example of a dehydropyridoannulene‐type macrocyclic scaffold with enforced exotopic ion‐coordination sites, and a detailed investigation into its ion‐binding and sensory behaviour 21a–21e. The latter studies revealed that 4 did indeed form coordination polymers, thereby acting as a precipitation sensor for a small group of transition metals.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Fluorescence Ion‐Sensory Properties of the First Dehydropyridoannulene‐Type Cyclophane with Enforced Exotopic Metal Ion Binding Sites

Baxter

2003

Chemistry A European J

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The new twistophane 4 has been synthesised, which comprises a conjugated dehydropyridoannulene-type macrocyclic scaffold with outwardly projecting nitrogen-donor sites for the purpose of metal ion coordination. The macrocyclíc structure of 4 was assigned by using spectroscopic methods, and shown to exist in a twisted and chiral ground state conformation by semi-empirical theoretical calculations. A detailed spectroscopic investigation into the metal ion binding properties of 4 and precursor 11 revealed that they functioned as selective complexants, affording a fluorescence quenching output response characteristic of Pd(II) and Hg(II) ions. Furthermore, 4 also signalled the presence of Fe(II), Co(II), Ni(II) and Ag(I) ions by the precipitation of coordination polymers, and exhibited reversible proton-triggered fluorescence quenching behaviour. Macrocycle 4 thus represents a unique type of molecular sensory platform, which may find a wealth of potential applications such as the detection of heavy-metal pollutants, as well as for the fabrication of proton-switchable materials and coordination polymers with novel electronic and magnetic properties.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Fluorescence Ion‐Sensory Properties of the First Dehydropyridoannulene‐Type Cyclophane with Enforced Exotopic Metal Ion Binding Sites

Baxter

2003

Chemistry A European J

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“…In light of the proposed location of redox processes, the addition of an electron forms, in all the species considered, a radical anion at one of the carbonyls with the negative charge largely localized on the oxygen and the radical center at the carbon. A known possible fate of reduced aromatic amides is the rupture of the C−N bond. However, fragmentation was proved not to occur to any significant extent by bulk electrolysis experiments (vide infra).…”

Section: Resultsmentioning

confidence: 99%

Electrochemically Induced Dynamics of a Benzylic Amide [2]Catenane

et al. 1999

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The electrochemistry of a benzylic amide [2]catenane was investigated and compared to that of its topologically trivial components. The redox behavior of both the catenane and the uninterlocked macrocycle can be largely understood in terms of the electrochemistry of smaller molecular fragments and simple molecular orbital considerations that show that the electroactivity of the CO groups is split into two sets of quasi-degenerate potentials separated by a substantial gap. A fast intermolecular reaction follows the reduction of the macrocycle and smaller fragments, consistent with the corresponding dimers containing a new C−C bond linking two reduced carbonyls. The cyclic voltammetric behavior of the catenane differs significantly from that of the macrocyclea feature that must therefore be directly attributable to the mechanically interlocked molecular architecture of the catenane. In particular, an intramolecular reaction (irreversible in the CV time scale) occurs in the catenane, which is shown to be a function of temperature and scan rate. Simulation of the cyclic voltammograms shows that the intramolecular reaction occurs on a time scale wider than that of circumrotation of the two rings in the neutral molecule, thus excluding that cyclic voltammetry (CV) is monitoring the latter process. Both the analysis of the electrochemical data and semiempirical quantum chemical (MNDO) calculations would suggest that the electrochemically induced reaction in the catenane is the soldering of the two interlocked macrocycles: the formation of a C−C bond between two reduced carbonyl groups would thus prevent further rotation of the two interlocked rings.

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“…In the case of the main part of the rotaxanes, decomposition was observed above 275 °C due to the deslipping pathway. 1 H and 13 C NMR spectra were recorded at 298 K on 200, 300, and 400 MHz spectrometers. 1 H NMR chemical shifts are reported relative to Me 4 Si and were referenced via residual proton resonances of the corresponding deuterated solvent, whereas 13 C NMR spectra are reported relative to Me 4 Si using the carbon signals of the deuterated solvent.…”

Section: Methodsmentioning

confidence: 99%

“…1 H and 13 C NMR spectra were recorded at 298 K on 200, 300, and 400 MHz spectrometers. 1 H NMR chemical shifts are reported relative to Me 4 Si and were referenced via residual proton resonances of the corresponding deuterated solvent, whereas 13 C NMR spectra are reported relative to Me 4 Si using the carbon signals of the deuterated solvent. Abbreviations of coupling patterns are as follows: br, broad; s, singlet; d, doublet; t, triplet; q, quadruplet; m, multiplet.…”

Section: Methodsmentioning

confidence: 99%

“…In order to circumvent this matter, Leigh et al were pioneers in describing the disassembly of hydrogen-bonded [2]rotaxanes through the transesterification of the stoppers of the thread for affording this type of rings. 7 Although alternative methods 12 for the preparation of benzylic amide macrocycles have been described in the literature, these procedures usually require multiple synthetic steps, 8,9,13 the previous preparation of templates, 7,14,15 or the use of organo-clay derivatives. 16 Herein, we propose an amenable approach based on the dethreading reaction 17,18 of tetraalkylsuccinamide-based [2]rotaxanes for the synthesis of a broad range of substituted benzylic amide macrocycles in which a dumbbell-shaped template can be recovered and indefinitely reused.…”

Section: Introductionmentioning

confidence: 99%

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Dethreading of Tetraalkylsuccinamide-Based [2]Rotaxanes for Preparing Benzylic Amide Macrocycles

et al. 2015

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The dethreading of a series of succinamide-based [2]rotaxanes bearing benzylic amide macrocycles is reported herein. These transformations proceeded quantitatively either under flash vacuum pyrolysis, conventional heating, or microwave irradiation. Studying the size complementarity of the stoppers at the ends of the thread and the cavity of the macrocycle allowed us to set up the best substituents for implementing the extrusion of the thread from the interlocked precursors. A variety of (1)H NMR kinetic experiments were carried out in order to evaluate the rate constants of the dethreading process, the half-life times of the rotaxanes, and the influence of temperature and solvents on these processes. The use of dibutylamino groups as stoppers yielded the rotaxane precursor in a reasonable yield and allowed the quantitative deslipping of the rotaxane. The overall process, including the rotaxane formation and its further dethreading, has been exploited for preparing benzylic amide macrocycles enhancing, in most cases, the results of the classical (2 + 2) condensation and other reported stepwise syntheses. The kinetics of the dethreading process is fairly sensitive to the electronic effects of the substituents on the isophthalamide unit or to the electronic nature of the pyridine rings through a conformational equilibrium expanding or contracting the cavity of the interlocked precursor.

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Syntheses and redox behavior of novel cyclic hosts having multiple redox centers of NAD+ analogue

Cited by 10 publications

References 8 publications

Synthesis and Fluorescence Ion‐Sensory Properties of the First Dehydropyridoannulene‐Type Cyclophane with Enforced Exotopic Metal Ion Binding Sites

Synthesis and Fluorescence Ion‐Sensory Properties of the First Dehydropyridoannulene‐Type Cyclophane with Enforced Exotopic Metal Ion Binding Sites

Electrochemically Induced Dynamics of a Benzylic Amide [2]Catenane

Dethreading of Tetraalkylsuccinamide-Based [2]Rotaxanes for Preparing Benzylic Amide Macrocycles

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