Selective and facile palladium-catalyzed amination of 2-fluoro-4- iodopyridine in the 4-position under microwave conditions

Synlett

Volumn , Issue 10, 2010, Pages 1505-1510

  Koley, Moumita ^a   Schnürch, Michael ^a   Mihovilovic, Marko D ^a  

^a VIENNA UNIVERSITY OF TECHNOLOGY   (Austria)

Author keywords

Amines; Catalysis; Cross coupling; Heterocycles; Regioselectivity

Indexed keywords

2 FLUORO 4 IODOPYRIDINE; AROMATIC AMINE; CARBON; NITROGEN; PALLADIUM; POTASSIUM CARBONATE; PYRIDINE DERIVATIVE; UNCLASSIFIED DRUG;

AMINATION; ARTICLE; CHEMICAL BOND; CHEMICAL STRUCTURE; CROSS COUPLING REACTION; GAS CHROMATOGRAPHY; MASS SPECTROMETRY; MICROWAVE RADIATION; TIME;

EID: 77953239171     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-0029-1219940     Document Type: Article

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39. General Procedure: 2-Fluoro-4-iodopyridine (4; 1 equiv), aryl/alkyl amine (1.2 equiv), K2CO3 (3.5 equiv), Pd(OAc)2 (2 mol%), and BINAP (2 mol%) were charged into a microwave vial and anhydrous toluene (2 mL) was added. The vial was then sealed, evacuated and flushed with argon. Then the reaction mixture was irradiated at 180 C in a CEM Explorer microwave unit for 30 min with stirring. After cooling to r.t., the solid material was removed by filtration and washed with CH2Cl2 (10 mL). The solvent was evaporated and the resulting crude product was purified by flash column chromatography. 2-Fluoro-N-phenylpyridin-4-amine (5a): Yellow solid; mp 148150 C; GC-MS: m/z (%) = 188 (100) [M]+, 187 (65), 167 (20); 1H NMR (CDCl3, 200 MHz): d = 6.45 (d, J = 1.7 Hz, 1 H), 6.676.78 (m, 2 H), 7.23 (d, J = 6.8 Hz, 3 H), 7.44 (t, J = 7.1 Hz, 2 H), 7.86 (d, J = 7.8 Hz, 1 H). 13C NMR (CDCl3, 50 MHz): d = 92.5 (q, JCF = 44.1 Hz), 108.2 (q, JCF = 3.1 Hz), 122.4 (d), 129.7 (d), 138.9 (s), 147.8 (d), 138.9 (s), 147.8 (q, JCF = 16.6 Hz), 154.5 (d, JCF = 3.1 Hz), 165.5 (d, JCF = 221.5 Hz). 2-Fluoro-N-(4- methoxyphenyl)pyridin-4-amine (5b): Yellow crystals; mp 150 C; GC-MS: m/z (%) = 218 (79)[M]+, 203 (100), 155 (13); 1H NMR (CDCl3, 200 MHz): d = 3.83 (s, 3 H), 6.20 (d, J = 1.7 Hz, 1 H), 6.31 (s, 1 H), 6.51 (td, J1 = 5.9 Hz, J2 = 1.9 Hz, 1 H)