OS(O)(=O)=O.[CH2:6]=[O:7].[CH3:8][C:9]1[C:18]2([CH2:20][CH2:19]2)[C@:17]([OH:22])([CH3:21])[C:15](=[O:16])[C:14]2[C:10]=1[C@@H:11](O)[C@@:12](CO)([CH3:23])[CH:13]=2>CC(C)=O>[CH3:23][C:12]1[CH:13]=[C:14]2[C:10](=[C:9]([CH3:8])[C:18]3([C@:17]([OH:22])([CH3:21])[C:15]2=[O:16])[CH2:20][CH2:19]3)[C:11]=1[CH2:6][OH:7]To a solution of 250 ml of 1M H2SO4 and 200 ml acetone was added 40 g paraformaldehyde (MW 30, 1.33 mol). The solution was heated to clear and was then allowed to cool to room temperature. 1 g illudin S (MW 264, 3.79 mmol) was added to the above solution. The mixture was stirred at room temperature for 72 h and was partitioned between ethyl acetate and water. The organic extracts were washed by saturated NaHCO3 and saline respectively to neutral. After being dried by MgSO4, the solution was concentrated and chromatographed to give 245 mg 14 (23.4%) and 226 mg HMAF (24.3%). 14 is a white crystal: mp 100.5-102.5; IR (KBr) 3469, 2966, 2858, 1703, 1656, 1596, 1172 cm−1; 1H NMR (CDCl3) δ0.48 (m, 1H), 0.84 (m, 1H), 0.99 (m, 1H), 1.10 (s, 3H), 1.17 (m, 1H), 1.32 (s, 3H), 1.67 (s, 3H), 3.61 (s, 1H), 3.73 (d, J=11.7 Hz, 1H), 3.96 (d, J=11.7 Hz, 1H), 4.56 (s, 1H), 4.75 (d, J=5.4 Hz, 1H), 4.91 (d, J=5.4 Hz, 1H), 6.52 (s, 1H); 13C NMR (CDCl3) δ199.7, 141.4, 136.5, 135.9, 134.7, 90.0, 80.3 75.9, 70.8, 46.8, 32.3, 24.7, 22.5, 13.8, 8.9, 5.6; MS m/z 276 (M+), 217, 201, 173; HRMS for C16H20O4 calcd 276.1362, found 276.1364; UV λmax 305 nm (ε3148).
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