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

Alle Artikel dieser Rubrik

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

Volltext

Referenzen

References

1 Stetter H. Frank W. Mertens R. Tetrahedron 1981, 37: 767

2a Costa J. Delgado R. Inorg. Chem. 1993, 32: 5257

2b Delgado R. Quintino S. Teixeira M. Zhang A. J. Chem. Soc., Dalton Trans. 1996, 55

2c Félix V. Costa J. Delgado R. Drew MGB. Duarte MT. Resende C. J. Chem. Soc., Dalton Trans. 2001, 1462

3 Kim WD. Hrncir DC. Kiefer GE. Sherry AD. Inorg. Chem. 1995, 34: 222

4 Aime S. Botta M. Crich SG. Giovenzana GB. Jommi G. Pagliarin R. Sisti M. Inorg. Chem. 1997, 36: 2992

5a Favre-Reguillon A. Segat-Dioury F. Nait-Bouda L. Cosma C. Siaugue J.-M. Foos J. Guy A. Synlett 2000, 868

5b Siaugue J.-M. Favre-Reguillon A. Dioury F. Plancque G. Foos J. Madic C. Moulin C. Guy A. Eur. J. Inorg. Chem. 2003, 2834

6a Herrera AM. Staples RJ. Kryatov SV. Nazarenko AY. Rybak-Akimova EV. J. Chem. Soc., Dalton Trans. 2003, 846

6b Herrera AM. Kalayda GV. Disch JS. Wilkstrom JP. Korendovych IV. Staples RJ. Campana CF. Nazarenko AY. Haas TE. Rybak-Akimova EV. J. Chem. Soc., Dalton Trans. 2003, 4482

7a Pandey GK. Srivastava S. Pandey OP. Sengupta SK. Indian J. Chem., Sect. A 1998, 447

7b Sharma K. Swaroop R. Singh RV. Heterocycl. Commun. 2001, 393

8a Denat F. Lacour S. Brandès S. Guilard R. Tetrahedron Lett. 1997, 38: 4417

8b Brandès S. Denat F. Lacour S. Rabiet F. Barbette F. Pullumbi P. Guilard R. Eur. J. Org. Chem. 1998, 2349

9 Lüning U. Liebigs Ann. Chem. 1987, 949

10a Beletskaya IP. Averin AD. Bessmertnykh AG. Guilard R. Tetrahedron Lett. 2001, 42: 4983

10b Beletskaya IP. Averin AD. Bessmertnykh AG. Guilard R. Tetrahedron Lett. 2001, 42: 4987

10c Beletskaya IP. Averin AD. Borisenko AA. Denat F. Guilard R. Tetrahedron Lett. 2003, 44: 1433

11 Wagaw S. Buchwald SL. J. Org. Chem. 1996, 61: 7240

12 Grasa GA. Viciu MS. Huang J. Nolan SP. J. Org. Chem. 2001, 66: 7729

13 Jonckers THM. Maes BUW. Lemiere GLF. Dommisse R. Tetrahedron 2001, 57: 7027

14 Maes BW. Loones KT. Jonckers TH. Lemiere GL. Dommisse R. Haemers A. Synlett 2002, 1995

15a Gradel B. Brenner E. Schneider R. Fort Y. Tetrahedron Lett. 2001, 42: 5689

15b Desmarets C. Schneider R. Fort Y. Tetrahedron Lett. 2001, 42: 247

15c Desmarets C. Schneider R. Fort Y. Tetrahedron 2001, 57: 7657

16 Wolfe JP. Buchwald SL. J. Org. Chem. 2000, 65: 1144

17a Den Hertog HJ. Wibaut JP. Recl. Trav. Chim. Pays-Bas 1936, 55: 122

17b Den Hertog HJ. de Jonge AP. Recl. Trav. Chim. Pays-Bas 1948, 67: 385

18 Wolfe JP. Tomori H. Sadighi JP. Yin J. Buchwald SL. J. Org. Chem. 2000, 65: 1158

19 Zhang X.-X. Buchwald SL. J. Org. Chem. 2000, 65: 8027

20

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.

21

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]⁺.