*3.4. Extraction Isolation*

The fungus was cultivated on PDA by adding 50 μM sodium butyrate at 28 ◦C for 7 days. Then, a single colony was inoculated in an autoclaved rice solid-substrate medium in Erlenmeyer flasks (130 × 1 L), each containing 100 g of rice, 100 mL of 0.3% of saline water, and 50 μM sodium butyrate and fermented at 28 ◦C for 28 days. Briefly, 130 flasks of cultures were extracted 3 times with 400 mL of EtOAc, and the filtrate was evaporated under reduced pressure to yield a crude extract of 20 g. The crude extracts were analyzed using HPLC and 1H NMR. The EtOAc extracts were chromatographed on silica gel column chromatography (CC) using a step gradient elution process with CH2Cl2-MeOH (0–100%) to provide nine fractions (Fr. 1–Fr. 9). Fr. 3 was subjected to open silica gel CC using

gradient elution with CH2Cl2-EtOAc (6:1–1:2, *v*/*v*) to yield seven fractions. Fr. 3.1–Fr. 3.7. Fr. 3.4 were purified with semi-preparative reversed-phase HPLC using MeOH-H2O (70:30, *v*/*v*) to afford compound **10** (6 mg) (Figures S38–S40) and compound **7** (6 mg) (Figures S29–S31). In addition, Fr. 3.5 was separated via silica gel CC using CH2Cl2-EtOAc (3:1, *v*/*v*) and purified via semi-preparative reversed-phase HPLC using MeOH-H2O (70:30, *v*/*v*) to afford compound **11** (7 mg) (Figures S41–S43). Fr. 4 was separated via open silica gel CC using gradient elution with CH2Cl2-EtOAc (3:1–1:1, *v*/*v*) to obtain three fractions (Fr. 4.1–Fr. 4.3). Fr. 4.2 was chromatographed on a Sephadex LH-20 CC by eluting with MeOH to yield three fractions (Fr. 4.2.1–Fr. 4.2.3). Fr. 4.2.1 was purified using a silica gel flash column with CH2Cl2-EtOAc (2:1, *v*/*v*) as the eluent to obtain compound **8** (11.8 mg) (Figures S32–S34) and compound **9** (3 mg) (Figures S35–S37). Fr. 4.2.2 was subjected to Sephadex LH-20 CC using MeOH-CH2Cl2 (1:1, *v*/*v*) as an eluent to obtain compound **6** (5.9 mg) (Figures S26–S28). Fr. 5 was subjected to open silica gel CC using gradient elution with CH2Cl2-EtOAc (4:1–1:2, *v*/*v*) to yield five fractions Fr. 5.1–Fr. 5.5. Fr. 5.3 was subsequently subjected to Sephadex LH-20 CC using MeOH-CH2Cl2 (1:1, *v*/*v*) as an eluent to give six fractions Fr. 5.3.1–Fr. 5.3.6. Fr. 6 was separated through silica gel elution using CH2Cl2-EtOAc (2:1, *v*/*v*) to obtain six fractions (Fr. 6.1–Fr. 6.6). Fr. 6.3 was purified with Sephadex LH-20 CC using MeOH-CH2Cl2 (1:1, *v*/*v*) to yield compound **4** (12 mg) (Figures S23–S25). Fr. 6.4 was subjected to reversed-phase HPLC (MeOH-H2O 70:30, *v*/*v*) to obtain compound **3** (5 mg) (Figures S20–S22). Fr. 6.5 was subjected to open silica gel CC using gradient elution with CH2Cl2-EtOAc (4:1–1:2, *v*/*v*) to give five fractions (Fr. 6.5.1–Fr. 6.5.5). Additionally, promising Fr. 6.5.4 was purified with reversed-phase HPLC (MeOH-H2O, 70:30 to 100:0, *v*/*v*) to furnish compound **2** (7 mg) (Figures S17–S19) and compound **1** (6 mg) (Figures S1–S8). Fr.7 was subjected to open silica gel CC using gradient elution with CH2Cl2-EtOAc (1:1, *v*/*v*) to yield six fractions Fr. 7.1–Fr. 7.6. Fr. 7.3 was subjected to Sephadex LH-20 CC using MeOH-CH2Cl2 (1:1, *v*/*v*) as an eluent to obtain compound **5** (15 mg) (Figures S9–S16).

Phaseolorin J (**1**): light yellow amorphous powder (MeOH); [α]20D +160 (*c* 0.0001, MeOH); UV (MeOH) λmax 214 nm (the absorptions due to aromatic rings); 1H and 13C NMR data, see Table 1; HRESIMS m/z 331.0781 [M + Na]+ (calcd for C15H16O7Na 331.0788).

Phomoparagin D (**5**): colorless amorphous powder (MeOH); [α]20D +60 (*c* 0.0001, MeOH); UV (MeOH) λmax 206 nm (the absorptions due to aromatic rings); 1H and 13C NMR data, see Table 1; HRESIMS *m/z* 506.2304 [M + K]+ (calcd for C28H37NO5K 506.2303).

#### *3.5. Theory and Calculation Details*

Specific Monte Carlo conformational searches were run by employing Spartan's 14 software using the Merck molecular force field (MMFF). Conformers with a Boltzmann population of over 0.4% were chosen for ECD (Tables S1–S4) and 13CNMR (Tables S5–S9) calculations. Then, the conformers were initially optimized at the B3LYP/6-31G(d) level in the gas phase using the PCM polarizable conductor calculation model. The stable conformations obtained at the B3LYP/6-31G(d) level were further used in magnetic shielding constants. The theoretical calculation of ECD was conducted in MeOH using the timedependent density functional theory (TD-DFT) at the B3LYP/6-31+g (d, p) level for all the conformers of compounds **1** and **5**. The ECD spectra were generated using the program SpecDis 1.6 (University of Würzburg, Würzburg, Germany) and GraphPad Prism 5 (University of California, San Diego, USA) from dipole-length rotational strengths by applying Gaussian band shapes with sigma = 0.3 eV.
