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Volumn 13, Issue 14, 2007, Pages 3964-3979

Nondegenerate π-donor/π-acceptor [2]catenanes containing proton-ionizable 1H-1,2,4-triazole subunits: Synthesis and spontaneous resolution

Author keywords

Catenanes; Self assembly; Spontaneous resolution; Supramolecular chemistry; Template synthesis

Indexed keywords

CHIRALITY; CIRCULAR DICHROISM SPECTROSCOPY; ION BOMBARDMENT; IONIZATION; MASS SPECTROMETRY; POLYETHERS; SELF ASSEMBLY; SUPRAMOLECULAR CHEMISTRY;

EID: 34250326177     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200601144     Document Type: Article
Times cited : (25)

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    • To our knowledge only two examples of zwitterionic rotaxanes have been reported: a based on α-cyclodextrin: R. Rahimah, A. E. Kaifer, J. Am. Chem. Soc. 1991, 113, 8188-8190;
    • To our knowledge only two examples of zwitterionic rotaxanes have been reported: a) based on α-cyclodextrin: R. Rahimah, A. E. Kaifer, J. Am. Chem. Soc. 1991, 113, 8188-8190;
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    • betainic[2]rotaxanes based on the use of transition metals: G. J. E. Davidson, S. J. Loeb, N. A. Parekh, J. A. Wisner, J. Chem. Soc. Dalton Trans. 2001, 3135-3136.
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    • 1H-1,2,4-triazole rings have been incorporated into crown ethers and macrocyclic frameworks: a J. S. Bradshaw, R. M. Izatt, Acc. Chem. Res. 1997, 30, 338-345;
    • 1H-1,2,4-triazole rings have been incorporated into crown ethers and macrocyclic frameworks: a) J. S. Bradshaw, R. M. Izatt, Acc. Chem. Res. 1997, 30, 338-345;
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    • Compound 1 (J. S. Bradshaw, R. B. Nielsen, P-K. Tse, G. Arena, B. E. Wilson, N. K. Dalley, J. D. Lamb, J. J. Christensen, R. M. Izatt, J. Heterocycl. Chem. 1986, 23, 361-368) was prepared by protection of 3,5-bis(chloromethyl)-1H-1,2,4-triazole hydrochloride (ref. [12]) with dihydropyrane in dichloromethane at room temperature.
    • Compound 1 (J. S. Bradshaw, R. B. Nielsen, P-K. Tse, G. Arena, B. E. Wilson, N. K. Dalley, J. D. Lamb, J. J. Christensen, R. M. Izatt, J. Heterocycl. Chem. 1986, 23, 361-368) was prepared by protection of 3,5-bis(chloromethyl)-1H-1,2,4-triazole hydrochloride (ref. [12]) with dihydropyrane in dichloromethane at room temperature.
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    • Formation of a [2]catenane incorporating two p-xylyl units in the macrocyclic polyether in 38% yield under similar experimental conditions indicates the lesser ability of the 1,2,4-triazole unit as template, 21c
    • [21c]
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    • 3,5-Dioxy-1H-1,2,4-triazole units are synthetically less accessible than the derivatives described here: A. Zumbrunn. Synthesis 1998, 1357-1361.
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    • Crystal data for 13·4PF6·2. 6MeCN·H2O: [C62H73N7O 10, PF6)4·2.6MeCN·H 2O, M, 1780.9, triclinic. P1 (no. 1, a, 12.215(1, b, 13.148(1, c, 14.137(1) Å, aα, 109.87(1, β, 103.31(1, γ, 102.17(1)°, V, 1971.5(2) Å3, Z, 1, ρcalcd, 1.500 gcm3, μ(CuKa, 1.96 mm1, T, 193 K, orange shards; 6437 independent measured reflections, F2 refinement, R1, 0.050, wR2, 0.133, 5966 independent observed reflections, F0|>4σ|F0, 2θ≤128°, 1136 parameters
    • 0|). 2θ≤128°) , 1136 parameters.
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    • Crystal data for 14·3.2PF6·0.8ClO 4·3MeCN: [C66H75N7O 10, PF6)3.2(ClO4) 0.8·3MeCN, M, 1793.0, triclinic, P1 (no. 1, a, 12.302(1, b, 13.807(2, c, 14.229(2) Å, a, 113.48(1, β, 102.84(1, γ, 104.33(1)°. V, 2003.1(4)Å3. Z, 1, ρcalcd, 1.486 gcm3, μ(CuKa, 1.96 mm-1, T, 183 K, red rhombs; 6407 independent measured reflections, F2 refinement, R1, 0.059, wR2, 0.160, 5806 independent observed reflections, F0/| > 4σ|F0, 2θ≤128°, 1195 parameters
    • 0|), 2θ≤128°), 1195 parameters.
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    • 2 using the SHELXTL program system a SHELXTL PC version 5.03, Siemens Analytical X-Ray Instruments, Inc, Madison, WI, 1994;
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    • + = +0.12(6)]. CCDC-190346 and CCDC-190347 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/datarequest/cif.
    • + = +0.12(6)]. CCDC-190346 and CCDC-190347 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/datarequest/cif.
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    • Analysis of the X-ray data for 14·4PF6 revealed that the fourth PF6 ion is overlaid by a partial-occupancy ClO4 ion in a ratio of about 20:80. We believe that the presence of this trace of ClO4 anion is a consequence of repeated recrystallization in glassware that had previously been contaminated with perchlorate
    • 4 anion is a consequence of repeated recrystallization in glassware that had previously been contaminated with perchlorate.
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    • [11] In the particular crystal that was chosen for examination by X-ray crystallography, all four naphthalene units had S chirality.
    • [11] In the particular crystal that was chosen for examination by X-ray crystallography, all four naphthalene units had S chirality.
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    • Interestingly, in a structure which contains both pyridyl and pyridinium rings, the stacking interactions involve the pyridyl ring: R. Prins, P. J. M. W. L. Birker, G. C. Verschoor, Acta Crystallogr. Sect. A 1982, 38, 2934-2935.
    • Interestingly, in a structure which contains both pyridyl and pyridinium rings, the stacking interactions involve the pyridyl ring: R. Prins, P. J. M. W. L. Birker, G. C. Verschoor, Acta Crystallogr. Sect. A 1982, 38, 2934-2935.
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    • Although stacking interactions between triazoles and pyridyl rings have been observed previously V. L. Rusinov. T. L. Pilicheva, A. A. Tumashow, G. G. Aleksandrov, E. O. Sidorow, I. V. Karpin, O. N. Chupakhin, Khim. Tekhnol. Vody Khim. Get. Soedin. 1990, 12, 1632-1637, so far as we can establish, none have been reported that involve either pyridinium or bipyridinium units
    • Although stacking interactions between triazoles and pyridyl rings have been observed previously (V. L. Rusinov. T. L. Pilicheva, A. A. Tumashow, G. G. Aleksandrov, E. O. Sidorow, I. V. Karpin, O. N. Chupakhin, Khim. Tekhnol. Vody Khim. Get. Soedin. 1990, 12, 1632-1637), so far as we can establish, none have been reported that involve either pyridinium or bipyridinium units.
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    • The extent of the spontaneous resolution process might depend not only on the catenane architecture hut also on the conditions of the crystallization; poor quality crystals obtained from an evaporating acetone solution led to only poor refinement factors from X-ray diffraction data. The collected data showed two independent molecules in a centrosymmetric monoclinic space group, that is, no spontaneous resolution had taken place. In this case, the crystals had grown under different conditions implying faster nucleation. This constitutes the first example of polymorphism in this family of compounds
    • The extent of the spontaneous resolution process might depend not only on the catenane architecture hut also on the conditions of the crystallization; poor quality crystals obtained from an evaporating acetone solution led to only poor refinement factors from X-ray diffraction data. The collected data showed two independent molecules in a centrosymmetric monoclinic space group, that is, no spontaneous resolution had taken place. In this case, the crystals had grown under different conditions implying faster nucleation. This constitutes the first example of polymorphism in this family of compounds.
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    • An equal numher of co-conformations are possible for the series of translational isomers containing 1H-1,2,4-triazole units inside the cavity of the tetracationic cyclophane
    • An equal numher of co-conformations are possible for the series of translational isomers containing 1H-1,2,4-triazole units inside the cavity of the tetracationic cyclophane.
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    • CD spectra of dissolved single crystals in solution in a range of temperatures from 25 to -40°C seem to indicate the preferential formation of one conformational enantiomer at low temperature, but the very low intensities of the Cotton effects indicate rapid isomerization upon dissolution.
    • CD spectra of dissolved single crystals in solution in a range of temperatures from 25 to -40°C seem to indicate the preferential formation of one conformational enantiomer at low temperature, but the very low intensities of the Cotton effects indicate rapid isomerization upon dissolution.
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    • S. Ramos, PhD Thesis, Faculty of Pharmacy, University of Barcelona (Spain), 2002.
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