NC1[C:8](I)=[CH:7][CH:6]=[CH:5][C:3]=1[NH2:4].[Cl:10][CH2:11][CH2:12][CH2:13][C:14]#[CH:15].C([N:18](CC)CC)C>[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cu]I>[Cl:10][CH2:11][CH2:12][CH2:13][C:14]#[C:15][C:5]1[C:3]([NH2:4])=[N:18][CH:8]=[CH:7][CH:6]=1To a stirred solution of 2-amino-3-iodoaniline (13 g) in triethylamine (260 ml) were added bis(triphenylphosphine) palladium dichloride (2 g) and copper (I) iodide (1.15 g). The mixture was cooled to 5° C. before the addition of 5-chloro-1-pentyne (6.6 ml). The mixture was heated to 50° C. and stirred 5 h. The mixture was cooled to room temperature, filtered and evaporated. The residue was purified by column chromatography on silica gel (ethyl acetate/hexane 1:1 to 5:1 eluant) to afford 3-(5-chloropent-1-ynyl)-pyridin-2-ylamine as a red oil (10.6 g, 92%): MS (EI) 196, 194 (M),159, 157, 131, 104; 1H NMR (δ, CDCl3) 8.0 (dd, 1H, J=2,5 Hz), 7.47 (dd, 1H, J=2,7 Hz), 6.59 (dd, 1H, J=5,7 Hz), 4.94 (br s, 1H), 3.72 (t,2H, J=6 Hz), 2.68 (t,2H, J=7 Hz), 2.07 (dt,2H, J=6,7 Hz) ppm.
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