CCO.C(Cl)(=O)C.[CH2:8]([O:15][C:16]1[CH:21]=[CH:20][C:19]([CH2:22][CH2:23][CH:24]([OH:27])[C:25]#[N:26])=[CH:18][CH:17]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.N[C:29]1[C:34]([OH:35])=[CH:33][CH:32]=[CH:31][N:30]=1>C(Cl)(Cl)Cl>[CH2:8]([O:15][C:16]1[CH:17]=[CH:18][C:19]([CH2:22][CH2:23][CH:24]([C:25]2[O:35][C:34]3[C:29]([N:26]=2)=[N:30][CH:31]=[CH:32][CH:33]=3)[OH:27])=[CH:20][CH:21]=1)[C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1A mixture of anhydrous EtOH (3.6 mL) and CHCl3 (4.0 mL) at 0° C. was treated with acetyl chloride (3.4 mL, 47.6 mmol, 16.2 equiv) and was stirred for 20 min. A solution of 4-(4-(benzyloxy)phenyl)-2-hydroxybutanenitrile (S50, 750 mg, 2.94 mmol, 1 equiv) in 9 mL of CHCl3 was added dropwise and the reaction was stirred for 20 h at 25° C. The reaction mixture was concentrated and the crude product was dissolved in anhydrous EtOH. 2-Amino-3-hydroxypyridine (370 mg, 3.36 mmol, 1.1 equiv) was added and the reaction mixture was warmed at reflux overnight. Concentration followed by column chromatography (SiO2, 2.5×8 cm, 0-4% MeOH—CHCl3 gradient) afforded S51 (130 mg, 0.36 mmol, 13%) as a tan oil: 1H NMR (CDCl3, 600 MHz) 8.52 (d, 1H, J=4.8 Hz), 7.78 (d, 1H, J=7.9 Hz), 7.43 (d, 2H, J=7.0 Hz), 7.39 (t, 2H, J=7.9 Hz), 7.34-7.31 (m, 1H), 7.28-7.26 (m, 1H), 7.14 (d, 2H, J=8.3 Hz), 6.87 (d, 2H, J=8.3 Hz), 5.07-5.00 (m, 1H), 5.00 (s, 2H), 2.84-2.81 (m, 2H), 2.36-2.30 (m, 2H); 13C NMR (CDCl3, 150 MHz) 157.0, 154.6, 146.1, 143.0, 137.0, 133.0 (2C), 129.4, 128.5, 127.8, 127.4, 120.2, 118.8, 114.7, 69.9, 67.0, 36.9, 30.1; IR (film) νmax 3380, 2926, 1665, 1612, 1557, 1511, 1454, 1410, 1382, 1239, 1177, 1092, 1026, 831, 785, 737, 700 cm−1.
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