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Volumn 46, Issue 23, 2007, Pages 4320-4324

DNA binding and catalytic properties of positively charged corroles

Author keywords

Corroles; DNA; Manganese; Peroxynitrite; Porphyrinoids; Structure elucidation

Indexed keywords

BINDING ENERGY; CATALYST ACTIVITY; CRYSTAL STRUCTURE; DNA; PORPHYRINS;

EID: 34447279248     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200700757     Document Type: Article
Times cited : (91)

References (53)
  • 1
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    • For the original syntheses of triarylcorroles, see: a
    • For the original syntheses of triarylcorroles, see: a) Z. Gross, N. Galili, I. Saltsman, Angew. Chem. 1999, 111, 1530;
    • (1999) Angew. Chem , vol.111 , pp. 1530
    • Gross, Z.1    Galili, N.2    Saltsman, I.3
  • 2
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    • Angew. Chem. Int. Ed. 1999, 38, 1427;
    • (1999) Chem. Int. Ed , vol.38 , pp. 1427
    • Angew1
  • 5
    • 0036284191 scopus 로고    scopus 로고
    • For reviews about corrole syntheses, see: d
    • For reviews about corrole syntheses, see: d) D. T. Gryko, Eur. J. Org. Chem. 2002, 1735;
    • (2002) Eur. J. Org. Chem , pp. 1735
    • Gryko, D.T.1
  • 7
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    • For modifications of triarylcorroles, see: a
    • For modifications of triarylcorroles, see: a) A. Mahammed, I. Goldberg, Z. Gross, Org. Lett. 2001, 3, 3443;
    • (2001) Org. Lett , vol.3 , pp. 3443
    • Mahammed, A.1    Goldberg, I.2    Gross, Z.3
  • 17
    • 0037266843 scopus 로고    scopus 로고
    • and references therein
    • R. F. Pasternack, Chirality 2003, 15, 329, and references therein.
    • (2003) Chirality , vol.15 , pp. 329
    • Pasternack, R.F.1
  • 23
    • 85170275121 scopus 로고    scopus 로고
    • Synthesis of 5: The required dipyrromethane (1.03 g) was prepared as in Ref. 15 (yield = 49%), but purified by two chromatographic treatments (alumina, dichloromethane/ethyl acetate 5:1, followed by silica gel, dichloromethane/ethyl acetate 10:0→10:1).
    • Synthesis of 5: The required dipyrromethane (1.03 g) was prepared as in Ref. 15 (yield = 49%), but purified by two chromatographic treatments (alumina, dichloromethane/ethyl acetate 5:1, followed by silica gel, dichloromethane/ethyl acetate 10:0→10:1).
  • 24
    • 85170214358 scopus 로고    scopus 로고
    • Synthesis of 4: Pentafluorobenzaldehyde (50 μL, 0,4 mmol) was added to a 10-mL solution of 5 (178 mg, 0.8 mmol) in propionic acid and the mixture was heated to reflux for 50 min. The residue obtained after solvent evaporation was washed with hot water, neutralized with ammonium hydroxide (25, and washed again with hot water. The solid material was dissolved in methanol, basic alumina was added, and the solvent was evaporated. Separation between 4 and the analogous porphyrin 2 was achieved by column chromatography (silica, CH2Cl2 followed by 0.5, methanol) followed by separation by preparative thin-layer chromatography (silica plate, CHCl3/MeOH 50:1) affording pure 4 (18 mg, 8, 4: Rf, 0.15 (CH2Cl2/ethyl acetate 1:1, UV/Vis (CH2Cl2/MeOH (2:1, λmax (ε 10-3, 416 (104.99, 576 (16.14, 610 (9.40, 640 5.34
    • 4J = 8.3 Hz, 4F).
  • 25
    • 85170271185 scopus 로고    scopus 로고
    • 3: 4-Pyridinecarboxaldehyde (38 μL, 0.40 mmol) was added to a 10-mL solution of 5 (178 mg, 0.8 mmol) in propionic acid, and the mixture was heated at reflux for 70 min. The residue obtained after solvent evaporation was washed with hot water, neutralized with ammonium hydroxide (25% ammonia, and washed again with hot water. The solid material was dissolved in methanol, basic alumina was added, and the solvent was evaporated. Separation of 3 was achieved by column chromatography (silica, CH2Cl2 followed by 0.5, methanol) followed by separation on PTLC (silica plate, CHCl 3/MeOH 100:1, The faster eluting fraction was comprised of the brownish red porphyrin (1) and the next slightly fluorescent dark-green-colored fraction afforded the desired corrole 3 6, 12 mg, Alternatively, good chromatographic separation could be achieved by eluting with ethyl acetate to which methanol was gradually added. Rf, 0.7
    • 6): δ = 7.87 (d, J = 5.1 Hz, 2H), 7.99 (d, J = 5.1 Hz, 4H), 8.35 (d, J = 4.8 Hz, 2H), 8.43 (d, J = 4.2 Hz, 2H), 8.66 (d, J = 4.8 Hz, 2H), 8.78 (d, J = 4.2 Hz, 2H), 9.02 ppm (br s, 6H).
  • 26
    • 85170273173 scopus 로고    scopus 로고
    • Manganese insertion: 2-Mn and 4-Mn were prepared by heating the porphyrin/corrole pyridine solution at reflux with 15 equivalents of Mn(OAc)2·4H2O followed by chromatographic separation (silica, starting with CH2Cl2 and gradually adding methanol, affording 92, and 81% yield, respectively. 2-Mn: UV/Vis (MeOH, λmax (ε10-3, 328 (12.6, 370 (22.5, 392 (19.5, 458 (49.7, 554 (5.2, 766 (0.84, MS (MALDI-TOF LD , m/z, 849 (100, M, 19F (MeOD, 188 MHz, δ, 134.49 (br s, 4F, 148.20 (s, 2F, 157.08 ppm (s, 4F, 4-Mn: UV/Vis (MeOH, λmax (ε10-3, 368 (16.7, 402 (26.7, 420 (4.8, 458 (18.4, 484 (16.2, 634 (9.4, MS (MALDI-TOF LD, m/z, 670 (100, M, 19F (C5D4N, 188 MHz, δ, 136.58 br s, 2F
    • 4N) (188 MHz): δ = -136.58 (br s, 2F), -155.16 (s, 1F), -161.23 ppm (s, 2F)
  • 27
    • 85170232825 scopus 로고    scopus 로고
    • N-methylation: 2-Mn and 4-Mn were dissolved in hot THF and excess methyl iodide was added to the solutions, which were then left at 40°C until complete precipitation. The solid material was collected by centrifugation and washed with THF and diethyl ether until the solvent was colorless, 2′)Mn(X)]2, UV/Vis (phosphate buffer solution; pH 6.8, λmax (ε10-3, 372 (22.4, 394 (19.7, 460 (56.4, 558 (5.7, MS (MALDI-TOF LD, m/z, 879 (10, M, 864 (100, M-15, 849 (50, M-30, 19F (MeOD, 188 MHz, δ, 137.87 (br s, 4F, 151.28 (s, 2F, 160.04 ppm (s, 4F, 4′)Mn]2, UV/Vis (KH2PO4 0.3 M, pH 6.8, λmax (ε10-3, 488 (49.4, 556 (8.4, 598 (10.3, 660 (15.9, MS (MALDI-TOF LD, m/z, 700 (10, M, 685 100
    • 19F (MeOD) (188 MHz): δ = -129.08 (br s, 2F), -152.51 (s, 1F), -158.68 ppm (s, 2F). The product was crystallized by slow diffusion of an n-hexane/diethyl ether mixture into concentrated methanol solution.
  • 28
    • 85170204651 scopus 로고    scopus 로고
    • 4′Mn]2+ was crystallized as a methanol and water solvate. Crystal data: 2(C37H22F5MnN 6)2+·4I-·5CH4O· H2O, M, 2086.92, triclinic, space group P1, a, 16.1423(4, b, 16.5311(4, c, 16.6329(5) Å, α, 115.329(1, β, 90.631(1, γ, 94.626(1)°, V, 3993.6(2) A°3, Z, 2, ρcalcd, 1.735 g cm -3, 45552 reflections measured, 15503 unique (Rint, 0.061, 2θmax, 52.0°, final R, 0.069 (wR, 0.177) for 10085 reflections with I > 2σ(I) and R, 0.112 (wR, 0.203) for all data. CCDC-634668 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
    • max = 52.0°), final R = 0.069 (wR = 0.177) for 10085 reflections with I > 2σ(I) and R = 0.112 (wR = 0.203) for all data. CCDC-634668 contains 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/ data_request/cif.
  • 31
    • 85170244124 scopus 로고    scopus 로고
    • [21]
    • [21]
  • 47
    • 85170212018 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2006, 45, 6544.
    • (2006) Chem. Int. Ed , vol.45 , pp. 6544
    • Angew1
  • 52
    • 85170241206 scopus 로고    scopus 로고
    • 2+ were dissolved in 10 mL of water (aided by 1 mL of methanol for the latter), 1.5 g of freshly HCl-regenerated ion-exchange resin (Dowex 1:8 chloride form) was added and the vessels were slowly shaken over night. The resin was filtrated and the solvent was lyophilized
    • 2+ were dissolved in 10 mL of water (aided by 1 mL of methanol for the latter), 1.5 g of freshly HCl-regenerated ion-exchange resin (Dowex 1:8 chloride form) was added and the vessels were slowly shaken over night. The resin was filtrated and the solvent was lyophilized
  • 53
    • 85170230833 scopus 로고    scopus 로고
    • [33] and the experimental procedures were identical to those reported in Ref. [31].
    • [33] and the experimental procedures were identical to those reported in Ref. [31].


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