Synthesis of New Polyazamacrocycles Incorporating the Pyridine Moiety

Irina P. Beletskaya; Alexei D. Averin; Nataliya A. Pleshkova; Anatolii A. Borisenko; Marina V. Serebryakova; Franck Denat; Roger Guilard

doi:10.1055/s-2004-836040

LETTER

Synthesis of New Polyazamacrocycles Incorporating the Pyridine Moiety

Irina P. Beletskaya*^a, Alexei D. Averin^a,c, Nataliya A. Pleshkova^a, Anatolii A. Borisenko^a, Marina V. Serebryakova^b, Franck Denat^c, Roger Guilard*^c
^a Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory, Moscow, 119992, Russia
Fax: +7(095)9393618; e-Mail: beletska@org.chem.msu.su;
^b V.N.Orekhovich Institute of Biomedical Chemistry, Pogodinskaya str., 10, Moscow, 119992, Russia
^c Laboratoire d’Ingénierie Moléculaire pour la Séparation et les Applications des Gaz (LIMSAG UMR5633), Faculté des Sciences Gabriel, 6, Bd. Gabriel, 21100 Dijon, France
Fax: +33(3)80396117; e-Mail: Roger.Guilard@u-bourgogne.fr;

Abstract

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Abstract

Polyazamacrocycles containing pyridine moieties have been synthesized through the Pd-catalyzed reaction of 2,6-dihalopyridines with various linear polyamines.

Key words

macrocycles - Pd catalysis - amines - arylation - aryl halides

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Referenzen

References

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Typical Procedure: An argon-flushed flask is charged with 2,6-dibromopyridine (1 mmol, 237 mg), 4-8 mol% Pd(dba)₂ (23-46 mg), 4.5-12 mol% BINAP (27-82 mg), appropriate polyamine (1-6 mmol), 5-100 mL of absolute dioxane, and NaOt-Bu (2.25-4 mmol). The mixture is refluxed for 5-22 h, cooled to ambient temperature and several drops of H₂O are added. Dioxane is evaporated in vacuo, the residue is taken up with CH₂Cl₂ (20 mL) and washed once with H₂O (10 mL), aqueous layer is extracted 3 times with CH₂Cl₂ (15 mL), combined organic fractions are dried over Na₂SO₄. CH₂Cl₂ is evaporated in vacuo, and crude material is chromatographed on a small amount of silica (4-5 mL) to minimize loss of the macrocycle, using a sequence of eluents: CH₂Cl₂, CH₂Cl₂-MeOH 100:1, 50:1, 25:1, 10:1, 3:1, CH₂Cl₂-MeOH-NH₃ (aq) 100:20:1, 100:20:2, 100:20:3, 10:3:1. Chromatography can be done without prior treatment of the reaction mixture with H₂O.

Selected spectroscopic data:
Compound 3a: mp 71-73 °C. IR (KBr): ν = 3254, 2937, 2879, 1604, 1521, 1459, 1361, 1340, 1261, 1240, 1143, 1106, 775, 724, 700 cm^-1. UV/Vis (MeOH): λ_max (ε) = 252 (11600), 320 (10400) nm. ¹H NMR (400 MHz, CDCl₃): δ = 1.71 (q, 4 H, J = 5.4 Hz), 2.63 (t, 4 H, J = 5.3 Hz), 2.68 (s, 4 H), 3.37 (q, 4 H, J = 5.2 Hz), 3.40 (br s, 2 H), 5.57 (d, 2 H, J = 7.9 Hz), 5.67 (br s, 2 H), 7.14 (t, 1 H, J = 7.9 Hz) ppm. ¹³C NMR (100.6 MHz, CDCl₃): δ = 30.2 (2 C), 40.5 (2 C), 47.4 (2 C), 49.3 (2 C), 94.0 (2 C), 138.7 (1 C), 158.8 (2 C) ppm. MS (70eV) m/z (%) = 249 (100) [M⁺], 162 (63), 148 (33), 136 (85), 123 (50). MALDI-TOF: m/z = 250.1 [M + H]⁺.
Compound 4a: oil. IR (KBr): ν = 3290, 2929, 2838, 1591, 1488, 1453, 1449, 1557, 1326, 1237, 1151, 1140, 1036, 886, 783, 729. UV/Vis (MeOH): λ_max (ε) = 246 (8600), 302 (5300) nm. ¹H NMR (400 MHz, CDCl₃): δ = 1.53 s (9 H), 1.63 (q, 2 H, J = 6.7 Hz), 1.78 (q, 2 H, J = 6.7 Hz), 2.11 (br s, 4 H), 2.68 (t, 2 H, J = 6.7 Hz), 2.72 (s, 4 H), 2.73 (t, 2 H, J = 6.7 Hz), 2.76 (t, 2 H, J = 6.7 Hz), 3.31 (t, 2 H, J = 6.7 Hz), 4.75 (br s, 1 H), 5.89 (d, 1 H, J = 7.4 Hz), 5.92 (d, 1 H, J = 7.6 Hz), 7.24 (t, 1 H, J = 7.9 Hz) ppm. ¹³C NMR (100.6 MHz, CDCl₃): δ = 28.8 (3 C), 29.5 (1 C), 33.6 (1 C), 40.1 (1 C), 40.6 (1 C), 47.5 (1 C), 47.8 (1 C), 49.2 (1 C), 49.3 (1 C), 78.4 (1 C), 97.8 (1 C), 100.2 (1 C), 139.2 (1 C), 157.3 (1 C), 163.0 (1 C) ppm. MALDI-TOF: m/z = 324.3 [M + H]⁺. Compound 7: oil. ¹H NMR (400 MHz, CDCl₃): δ = 1.79 (q, 4 H, J = 6.3 Hz), 2.75 (t, 4 H, J = 6.3 Hz), 2.76 (s, 4 H), 3.34 (t, 4 H, J = 6.3 Hz), 5.38 (br s, 2 H), 6.25 (d, 2 H, J = 8.2 Hz), 6.52 (d, 2 H, J = 7.7 Hz), 7.29 (t, 2 H, J = 8.0 Hz) ppm; two NH protons were not assigned. ¹³C NMR (100.6 MHz, CDCl₃): δ = 28.9 (2 C), 40.7 (2 C), 47.6 (2 C), 48.8 (2 C), 104.5 (2 C), 111.4 (2 C), 139.5 (2 C), 147.8 (2 C), 158.9 (2 C) ppm. MALDI-TOF: m/z = 397.6 [M + H]⁺.