Reaction Steps
A suspension of tert-BuOK (505 mg, 4.5 mmol) in anhydrous toluene (4.5 mL) was refluxed (1 h) and then an anhydrous toluene solution (1.5 mL) of 15a (386 mg, 1.5 mmol) was added (20 min) and the reaction mixture was refluxed for an additional 3 h, and then cooled. EtOH (2 mL) was added, and the reaction was filtered (Celite pad) and concentrated in vacuo. The residue was purified by PTLC (5% MeOH—CHCl3) to give 4 (127 mg, 40%) as a yellow oil: Rf 0.21 (5% MeOH—CHCl3); IR (neat) 2932, 2857, 1656, 1292, 1207 cm−1; 1H NMR (CDCl3, 500 MHz) δ 1.25 (t, J=7.1 Hz, 3H, CH2CH3), 1.55-1.64 (m, 2H, C(7)H2), 1.65-1.73 (m, 1H), C(6)HH′), 1.84-1.86 (m, 1H, C(6)HH′), 2.19 (br s, 1H, C(5)H), 2.89 (d, J=13.0 Hz, 1H), C(9)HH′), 2.90-2.96 (m, 2H, C(8)H2), 2.96 (d, J=13.0 Hz, 1H, C(9)HH′), 3.24 (d, J=16.8 Hz, 1H, C(2)HH′), 3.73 (d, J=16.8 Hz, 1H, C(2)HH′), 4.17 (q, J=7.1 Hz, 2H, CH2CH3), 11.83 (br s, 1H, C(4)OH), the 1H NMR assignments were consistent with the COSY spectrum; 13C NMR (CDCl3, 150 MHz) 14.2 (CH2CH3), 19.1 (C(7)), 26.6 (C(6)), 32.2 (C(5)), 49.5 (C(2)), 51.4 (C(9)), 55.2 (C(8)), 60.2 (CH2CH3), 99.3 (C(3)), 170.6 (C(O)), 172.1 (C(4) ppm, the assignments were consistent with the DEPT, HMQC and HMBC spectra; MS (+CI) 212 [M+1]+; Mr (+CI) 212.128 08 [M+1]+ (calcd for C11H18NO3 212.128 67). Anal. (C11H17NO3): C, H, N.
