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27 All compounds showed satisfactory spectroscopic data as well as microanalytical data. Diastereomeric ratios were established from the 1H NMR spectrum of the crude product.
Experimental procedure for the preparation of 11: A solution of 10 (0.75 g, 2.53 mmol) in 1,2,4-trichlorobenzene (50 mL) was stirred under argon at 200 °C for 24 h. After cooling, the solvent was removed under reduced pressure (0.2 Torr). The resulting oil was purified by flash chromatography on silica gel (EtOAc-Et2O, 2:8 to 5:5) to afford compounds 11a (0.336 g; 41%), 11b (0.232 g; 29%), and 11c (0.12 g; 15%) in 85% overall yield.
11a: White solid; mp 146-147 °C. IR (film): 3083, 2932, 1773, 1610 cm-1. 1H NMR (500 MHz, CDCl3): δ = 1.30 (d, J = 11.9 Hz, 1 H), 1.52 (m, 3 H), 1.92 (m, 3 H), 2.14 (m, 3 H), 2.73 (d, J = 3.8 Hz, 1 H), 2.76 (m, 1 H), 2.84 (dt, J = 8.5 Hz, J = 12.4 Hz, 1 H), 3.23 (m, 1 H), 3.34 (m, 1 H), 4.98 (m, 2 H), 5.42 (m, 1 H), 7.06 (d, J = 5.3 Hz, 1 H), 8.35 (m, 2 H). 13C NMR (250 MHz, CDCl3): δ = 21.6, 23.8, 27.5; 28.9, 34.2, 35.1, 37.0, 43.2, 44.8, 49.1, 96.7, 116.6, 121.3, 132.7, 137.2, 144.1, 147.5, 151.0, 177.2. Anal. Calcd for C19H21NO2: C, 77.26; H, 7.17. Found: C, 77.48; H, 7.26.
11b: Oil. IR (film): 2930, 2880, 1762, 1550 cm-1. 1H NMR (500 MHz, CDCl3) : δ = 1.49 (m, 1 H), 1.62 (m, 1 H), 1.64 (m, 1 H), 1.69 (m, 1 H), 1.71 (m, 1 H), 1.80 (d, J = 11.8 Hz, 1 H), 2.03 (m, 1 H), 2.12 (m, 1 H), 2.26 (m, 1 H), 2.52 (dd, J = 5.4, 11.8 Hz, 1 H), 2.65 (d, J = 10.5 Hz, 1 H), 2.89 (m, 1 H), 3.44 (d, J = 5.4 Hz, 1 H), 5.11 (d, J = 9.5 Hz, 1 H), 5.14 (d, J = 17.0 Hz, 1 H), 5.64 (dt, J = 9.9, 17.2 Hz, 1 H), 7.32 (d, J = 5.0 Hz, 1 H), 8.34 (s, 1 H), 8.39 (d, J = 5.0 Hz, 1 H). 13C NMR (250 MHz, CDCl3): δ = 25.8, 27.0, 27.1, 29.5, 38.9, 40.4, 41.7, 43.8, 49.1, 49.4, 96.3, 116.7, 119.8, 132.0, 137.2, 144.4, 147.1, 150.4, 175.5. HRMS (EI): m/z calcd for C19H21NO2 [M+]: 295.1572; found: 295.1571.
11c: Oil. IR (film): 2928, 1771, 1609 cm-1. 1H NMR (500 MHz, CDCl3): δ = 1.09 (qd, J = 5.7, 12.2 Hz, 1 H), 1.49 (qd, J = 2.7, 11.1 Hz, 1 H), 1.59 (m, 1 H), 1.91 (m, 2 H), 2.01 (d, J = 12.2 Hz, 1 H), 2.07 (dd, J = 4.2, 12.2 Hz, 1 H), 2.08 (m, 1 H), 2.12 (qd, J = 5.4, 11.9 Hz, 1 H), 2.12 (m, 1 H), 2.45 (td, J = 7.6, 11.3 Hz, 1 H), 2.90 (m, 1 H), 5.09 (m, 1 H), 5.88 (m, 1 H), 7.18 (d, J = 5.1 Hz, 1 H), 8.32 (s, 1 H), 8.37 (d, J = 5.1 Hz, 1 H). 13C NMR (250 MHz, CDCl3): δ = 25.7, 26.7, 29.8, 31.6, 32.9, 39.5, 39.8, 41.0, 51.4, 51.9, 94.3, 116.7, 119.0, 132.4, 135.4, 147.2, 147.5, 150.3, 179.7. HRMS (EI): m/z calcd for C19H21NO2 [M+]: 295.1572; found: 295.1569.
