*3.4. Extraction and Isolation*

The fermented rice substrate was mechanically fragmented after incubation, and then extracted with petroleum ether (PE) to remove the low-polarity chemical constituents. The remaining culture was extracted thoroughly with EtOAc, which was filtered and evaporated under reduced pressure to give EtOAc extract (75.5 g).

The EtOAc extract was fractionated by Si gel VLC (vacuum liquid chromatography), using solvents of increasing polarity (PE-EtOAc, 20:1 to 1:1, and then CH2Cl2-MeOH, 20:1 to 1:1) to yield nine fractions (Frs. 1−9). Fr. 5 (6.6 g) was further separated by CC (Column Chromatography) over Lobar LiChroprep RP-18 with a MeOH-H2O gradient (from 1:9 to 10:0) to yield 10 subfractions (Frs. 5.1−5.10). Fr. 5.4 (453.8 mg) was subjected to CC on Si gel eluting with a CH2Cl2-MeOH gradient (from 500:1 to 200:1) to yield compounds **6** (187.6 mg) and **7** (15.5 mg). Fr. 6 (29.2 g) was repeatedly subjected to Si gel VLC and then fractionated by solvents of increasing polarity from CH2Cl2 to acetone to yield

four subfractions (Frs. 6.1−6.4) based on HPLC and TLC analysis. Purification of Fr. 6.1 (6.2 g) by CC over Lobar LiChroprep RP-18 with a MeOH-H2O gradient (from 1:9 to 10:0) yielded 10 subfractions (Frs. 6.1.1−6.1.10). Fr. 6.1.1 (14.3 mg) was recrystallized from mixed solvents (MeOH-H2O, 10:1) to give **3** (6.7 mg). Fr. 6.1.2 (53.7 mg) was purified by prep-TLC and CC on Sephadex LH-20 (MeOH) to obtain **10** (34.1 mg). Fr. 6.1.3 (44.8 mg) was also recrystallized from MeOH to give **9** (21.9 mg). Fr. 6.1.4 (79.2 mg) was applied to semi-preparative HPLC (Elite ODS-BP column, 10 μm; 20 × 250 mm; 70% MeOH-H2O, 16 mL/min) to afford **4** (18.3 mg, *t*<sup>R</sup> 29.6 min). Fr. 6.1. 5 (207.3 mg) was subjected to repeated CC on silica gel (CH2Cl2-MeOH, 140:1) and purified by prep-TLC and CC on Sephadex LH-20 (MeOH) to give **5** (9.4 mg). Fr. 6.2 (6.0 g) was split by CC over Lobar LiChroprep RP-18, silica gel, and Sephadex LH-20 to yield **2** (12.5 mg). Fr. 6.3 (6.5 g) was subjected to CC over Lobar LiChroprep RP-18, eluted with a MeOH-H2O gradient (from 1:9 to 10:0) to yield 10 subfractions (Frs. 6.3.1−6.3.10). Fr. 6.3.1 (32.1 mg) was recrystallized from mixed solvents (MeOH-H2O, 10:1) to afford **8** (13.7 mg). Fr. 6.3.3 (108.9 mg) was purified by semi-preparative HPLC (Elite ODS-BP column, 10 μm; 20 × 250 mm; 72% MeOH-H2O, 16 mL/min) to afford **1** (46.8 mg, *t*<sup>R</sup> 31.2 min).

5'-Hydroxy-6'-ene-epicoccin G (**1**): Colorless cube crystal (MeOH-H2O); mp 161–163 ◦C; [α] D <sup>25</sup> −95.7 (*c* 0.23, MeOH); UV (MeOH) λmax (log ε) 204 (3.99) nm; ECD (4.18 mM, MeOH) λmax (Δε) 200 (−1.96), 233 (+2.46), 260 (−3.07) nm; 1H and 13C NMR data, Tables <sup>1</sup> and 2; ESIMS *<sup>m</sup>*/*<sup>z</sup>* 455 [M <sup>+</sup> H]+; HRESIMS *m*/*z* 455.1293 [M + H]<sup>+</sup> (calcd for C20H27O6N2S2, 455.1305).

7-Methoxy-7'-hydroxyepicoccin G (**2**): Colorless cube crystal (MeOH); mp 173–175 ◦C; [α] D <sup>25</sup> −138.9 (*c* 0.18, MeOH); UV (MeOH) λmax (log ε) 204 (4.16) nm; ECD (4.80 mM, MeOH) λmax (Δε) 200 (−3.35), 231 (+3.91), 259 (−2.53)nm; 1H and 13C NMR data, Tables <sup>1</sup> and 2; ESIMS *<sup>m</sup>*/*<sup>z</sup>* 501 [M <sup>+</sup> H]+; HRESIMS *m*/*z* 501.1360 [M + H]<sup>+</sup> (calcd for C21H29O8N2S2, 501.1360).

8'-Acetoxyepicoccin D (**3**): Colorless needle crystal (MeOH); mp 233–235 ◦C; [α] D <sup>25</sup> +225.6 (*c* 0.02, MeOH); UV (MeOH) λmax (log ε) 204 (3.75) nm; ECD (2.15 mM, MeOH) λmax (Δε) 218 (+1.24), 252 (+0.31), 290 (−0.10) nm; 1H and 13C NMR data, Tables 1 and 2; ESIMS *m*/*z* 482 [M + NH4] <sup>+</sup>, *m*/*z* 487 [M + Na]+; HRESIMS *m*/*z* 482.1045 [M + NH4] <sup>+</sup> (calcd for C20H24O7N3S2, 482.1050), 487.0601 [M + Na]<sup>+</sup> (calcd for C20H20O7N2NaS2, 487.0604).

7'-Demethoxyrostratin C (**4**): Colorless amorphous powder; [α] D <sup>25</sup> −215.4 (*c* 0.13, MeOH); UV (MeOH) <sup>λ</sup>max (log <sup>ε</sup>) 201 (4.06) nm; ECD (2.20 mM, MeOH) <sup>λ</sup>max (Δε) 200 (+0.43), 234 (−2.24), 265 (+0.53) nm; 1H and 13C NMR data, Tables <sup>1</sup> and 2; ESIMS *<sup>m</sup>*/*<sup>z</sup>* 455 [M <sup>+</sup> H]+; HRESIMS *<sup>m</sup>*/*<sup>z</sup>* 455.0930 [M <sup>+</sup> H]<sup>+</sup> (calcd for C19H23O7N2S2, 455.0941).

(±)-5-Hydroxydiphenylalazine A (**5**): Yellow oil; UV (MeOH) λmax (log ε) 200 (4.49) nm, 216 (4.19) nm, 283 (4.14) nm; 1H and 13C NMR data, Tables 1 and 2; ESIMS *m*/*z* 323 [M + H]+; HRESIMS *m*/*z* 323.1383 [M + H]<sup>+</sup> (calcd for C19H19O3N2, 323.1390).

(+)-**5**: [α] D <sup>25</sup> +350 (*c* 0.18, MeOH); ECD (5.59 mM, MeOH) λmax (Δε) 209 (+2.59), 233 (+1.11), 291 (+2.41) nm.

(−)-**5**: [α] D <sup>25</sup> −345 (*c* 0.18, MeOH); ECD (5.59 mM, MeOH) λmax (Δε) 206 (−3.11), 242 (−1.21), 288 (−2.55) nm.
