Reaction Steps
A solution of ester 12e (0.29 g, 1.493 mmol) in 5.3 mL dry CH2Cl2 was cooled to -78° C. and treated with DIBAL (1.0M solution in dry CH2Cl2, 1.5 mL, 1.493 mmol, 1.0 equiv), then an additional 0.7 mL DIBAL (0.5 equiv) solution was added and the reaction was quenched immediately upon completion by tlc with 2.0 mL dry CH3OH. The reaction mixture was diluted with 5 mL saturated aqueous sodium potassium tartrate and warmed gradually to room temperature, partitioned, and extracted with CH2Cl2 (3×5 mL). The combined extracts were washed with saturated aqueous sodium potassium tartrate (3×5 mL), dried (MgSO4), filtered and concentrated in vacuo. SGC chromatotron (SiO2, 4 mm, 0-10% CH3OH/CHCl3) afforded 13e (0.213 g, 0.224 g theoretical, 95%). For 13e: 1H NMR (CDCl3, 250 MHz) d 9.75 (s, 1H, CHO), 8.52 (br d, 1H, J=1.5 Hz, Pyr C3-H), 8.44 (dd, 1H, J=1.5, 2.5 Hz, Pyr C5-H), 8.38 (d, 1H, J=2.5 Hz, Pyr C6-H), 3.55 (ddq, 1H, J=6.0, 7.0, 7.9 Hz, CHCH3), 3.08 (ddd, 1H, J=1.2, 7.9, 17.8 Hz, CHH), 2.73 (ddd, 1H, J=1.2, 6.0, 17.8 Hz, CHH), 1.33 (d, 3H, J=7.0 Hz, CH3); 13C NMR (CDCl3 , 125 MHz) d 200.8, 158.2, 144.1, 143.8, 142.6, 49.3, 33.2, 20.8; IR (neat) nmax 3054, 2966, 1722, 1668, 1525, 1471, 1406, 1294, 1147, 1117, 1016, 848, 769 cm-1. See FIG. 19a.
