*3.2. Fungal Materials*

The fungus TGGP35 was isolated from the stem of the mangrove plant *Acanthus ilicifolius*, which were collected in the Dongzhai Port, Haikou, Hainan Province in August, 2015. The fungus was identified according to its morphological characteristics and a molecular biological protocol by 18S rRNA amplification and sequencing of the ITS region. The sequence data have been submitted to GeneBank, with accession number MT071116, and the fungal strain was identified as *Talaromyces flavus* (Eurotiales: Trichocomaceae). The strains have been stored in the Key Laboratory of Tropical Medicinal Resources Chemistry of the Ministry of Education, School of Chemistry and Chemical Engineering, Hainan Normal University (PDA medium, stored at 4 ◦C).

#### *3.3. Fermentation, Extraction and Isolation*

The seed culture was prepared in potato liquid medium (6 g sea salt and 10 g peptone in 2 L of potato infusion, in 1 L × 4 erlenmeyer flasks each containing 500 mL seed medium), and incubated on a rotary shaker (170 rpm) for 4 days at 28 ◦C. In total, 20 mL seed culture was then transferred into 1 L erlenmeyer flasks with solid rice medium with a total of 100 bottles of fermentation (each flask contained 60 mL rice, 0.6 g sea salt and 1.0 g peptone) at 28 ◦C for 4 weeks. The whole rice fermented material was extracted three times with EtOAc, and then concentrated in vacuo to yield crude extracts (120.8 g). The total crude extracts were subjected to silica gel column chromatography (CC) eluted with petroleum ether/EtOAc (*v*/*<sup>v</sup>*, gradient 100:0–0:100) and EtOAc/MeOH (*v*/*<sup>v</sup>*, gradient 100:0–70:30) to generate fifteen fractions (Fr. A-Fr. L). Fr. F (20.5 g) was fractionated by silica gel CC (200-300 mesh) using a gradient elution of petroleum ether/EtOAc system (7:1–0:1) to obtain ten fractions (Fr. F1-Fr. F10) by the TLC analysis. Fr. F2 (10.3 g) was subjected to Sephadex LH-20 (Petroleum ether-CHCl3-MeOH, 2:1:1, *v*/*v*), and then to semi-preparative HPLC (MeOH-H2O, 70:30, *v*/*v*) to give compounds **1** (4.2 mg), **2** (5.5 mg), **3** (3.8 mg), **5** (4.5 mg) and **7** (4.7 mg). Subfraction Fr. F3 was further separated by semi-preparative HPLC (MeOH-H2O, 60:40, *v*/*v*) for four subfractions Fr. F3a-3d. Compounds **6** (4.7 mg), **8** (5.5 mg), **9** (5.8 mg), and **10** (3.5 mg) were isolated from subfraction Fr. F3a. Compounds **11** (3.7 mg), **14** (4.7 mg), **16** (5.5 mg), **17** (5.8 mg) and **19** (3.5 mg) for subfraction Fr. F3b. Compounds **12** (6.3 mg), **13** (3.2 mg) and **15** (5.7 mg) for subfraction Fr. F3c, and compounds

**18** (6.8 mg), **19** (6.2 mg) and **21** (3.6 mg) for subfraction Fr. F3d. Fr. F4 (5.4 g) were subjected to Sephadex LH-20 (CHCl3-MeOH, 1:1, *v*/*v*), then used for semi-preparative HPLC (MeOH-H2O, 65:35, *v*/*v*) to give compound **20** (3.0 mg). Fr. F5 (2.4 g) was subjected to Sephadex LH-20 (CHCl3-MeOH, 1:1, *v*/*v*), then used for semi-preparative HPLC (MeOH-H2O, 35:65, *v*/*v*) to give compounds **22** (3.4 mg) and **23** (2.7 mg).

*Talaromarin A* (**1**): yellow oil; [*α*]25D −21.4 (*c* 0.10, MeOH); UV (MeOH) *λ*max (log *ε*) 330, 221 nm; IR (KBr) *ν*max 3432, 1716, 1618, 1383 cm<sup>−</sup>1; CD (*c* 0.05, MeOH) *λ*max (Δ*ε*) 243 (+5.68), 266 (−2.89) nm; 1H and 13C NMR data see Tables 1 and 2; HR-ESI-MS *m*/*z*: 323.1475 [M + H]+, (C17H23O6, calcd. for 323.1472).

*Talaromarin B* (**2**): white powder; [*α*]25D −23.6 (*c* 0.10, MeOH); UV (MeOH) *λ*max (log *ε*) 330, 255, 223 nm; IR (KBr) *ν*max 3414, 1668, 1619, 1586, 1502, 1442 cm<sup>−</sup>1; CD (*c* 0.05, MeOH) *λ*max (Δ*ε*) 244 (+2.27), 265 (−2.17) nm; 1H and 13C NMR data see Tables 1 and 2; HR-ESI-MS *m*/*z*: 279.1240 [M − H]<sup>−</sup>, (C15H19O5, calcd. for 279.1239).

*Talaromarin C* (**3**): yellow oil; [*α*]25D −22.0 (*c* 0.10, MeOH); UV (MeOH) *λ*max (log *ε*) 317, 215 nm; IR (KBr) *ν*max 3415, 1638, 1618, 1384 cm<sup>−</sup>1; CD (*c* 0.05, MeOH) *λ*max (Δ*ε*) 248 (+1.36), 266 (−2.01) nm; 1H and 13C NMR data see Tables 1 and 2; HR-ESI-MS *m*/*z*: 311.1485 [M + H]+, (C16H23O6, calcd. for 311.1482).

*Talaromarin D* (**4**): yellow oil; [*α*]25D −21.8 (*c* 0.10, MeOH); UV (MeOH) *λ*max (log *ε*) 313, 222 nm; IR (KBr) *ν*max 3475, 1706, 1637, 1617 cm<sup>−</sup>1; CD (*c* 0.05, MeOH) *λ*max (Δ*ε*) 243 (−0.31), 259 (−6.25) nm; 1H and 13C NMR data see Tables 1 and 2; HR-ESI-MS *m*/*z*: 295.1527 [M + H]+, (C16H23O5, calcd. for 295.1524).

*Talaromarin E* (**5**): colorless oil; [*α*]25D −24.4 (*c* 0.10, MeOH); UV (MeOH) *λ*max (log *ε*) 314, 219 nm; IR (KBr) *ν*max 1638,1617 cm<sup>−</sup>1; CD (*c* 0.05, MeOH) *λ*max (Δ*ε*) 245 (+3.93), 264 (−11.89) nm; 1H and 13C NMR data see Tables 1 and 2; HR-ESI-MS *m*/*z*: 293.1370 [M + H]+, (C16H21O5, calcd. for 293.1374).

*Talaromarin F* (**6**): yellow oil; [*α*]25D −21.2 (*c* 0.10, MeOH); UV (MeOH) *λ*max (log *ε*) 328, 254, 223 nm; IR (KBr) *ν*max 3481, 3407, 1736, 1671 cm<sup>−</sup>1; CD (*c* 0.05, MeOH) *λ*max (Δ*ε*) 238 (+10.12), 267 (−2.07) nm; 1H and 13C NMR data see Tables 1 and 2; HR-ESI-MS *m*/*z*: 265.1050 [M + H]+, (C14H17O5, calcd. for 265.1053).

#### *3.4. Preparations of the (S)- and (R)-MTPA Esters of Compounds* **1***,* **2** *and* **3**

Compound **1** was hydrolyzed in anhydrous ethanol solution for 90 min with potassium carbonate in an equivalent ratio of 1:2; the mixed product after hydrolysis was purified by semi-preparative HPLC (MeOH-H2O, 70:30, *v*/*v*) to obtain **1a**. The preparation of (*S*)- and (*R*)-MTPA ester derivatives of **1a**, **2** and **3** was performed as described previously [28].

Hydrolysate of **1** (**1a**): 1H NMR (CDCl3, 400 MHz): *δ*H 6.99 (1H, d, *J* = 8.8 Hz H-6), 6.79 (1H, d, *J* = 8.8 Hz, H-7), 4.26 (1H, m, H-3), 3.83 (1H, m, H-4-), 3.10 and 2.63 (2H, m, H-4), 1.90 (2H, m, H-1-), 1.70 (2H, m, H-2-), 1.50 (2H, m, H-3-), 1.21 (3H, d, *J* = 6.0 Hz, H-5-); 13C NMR (CDCl3, 100 MHz): *δ*C 163.3, 159.4, 151.5, 145.1, 135.0, 128.5, 121.2, 111.4, 68.2, 56.6, 39.1, 34.9, 28.0, 23.8, 21.4; ESI-MS *m*/*z* 281.1 [M + H]+.

(*S*)-MTPA ester of **1a**: 1H NMR (CDCl3, 600 MHz): *δ*H 7.29 (1H, d, *J* = 9.0 Hz, H-6), 6.94 (1H, d, *J* = 9.0 Hz, H-7), 5.12 (1H, m, H-4-), 4.21 (1H, m, H-3), 2.64 and 2.49 (2H, m, H-4), 1.86 (2H, m, H-1-), 1.67 (2H, m, H-2-), 1.55 (2H, m, H-3-), 1.25 (3H, d, *J* = 6.6 Hz, H-5-); ESI-MS *m*/*z* 758.2 [M + Na]+.

(*R*)-MTPA ester of **1a**: 1H NMR (CDCl3, 600 MHz): *δ*H 7.31 (1H, d, *J* = 9.0 Hz, H-6), 6.94 (1H, d, *J* = 9.0 Hz, H-7), 5.11 (1H, m, H-4-), 4.09 (1H, m, H-3), 2.62 and 2.41 (2H, m, H-4), 1.83 (2H, m, H-1-), 1.64 (2H, m, H-2-), 1.53 (2H, m, H-3-), 1.33 (3H, d, *J* = 6.0 Hz, H-5-); ESI-MS *m*/*z* 758.2 [M + Na]+.

(*S*)-MTPA ester of **2**: 1H NMR (CDCl3, 600 MHz): *δ*H 7.01 (1H, d, *J* = 7.8 Hz, H-5), 6.63 (1H, d, *J* = 7.8 Hz, H-6), 5.17 (1H, m, H-4-), 4.52 (1H, m, H-3), 2.82 (2H, m, H-4), 1.88 (2H, m, H-1-), 1.62 (2H, m, H-2-), 1.50 (2H, m, H-3-), 1.29 (3H, d, *J* = 6.0 Hz, H-5-); ESI-MS *m*/*z* 758.3 [M + Na]+.

(*R*)-MTPA ester of **2**: 1H NMR (CDCl3, 600 MHz): *δ*H 7.01 (1H, d, *J* = 8.4 Hz, H-5), 6.62 (1H, d, *J* = 8.4 Hz, H-6), 5.16 (1H, m, H-4-), 4.42 (1H, m, H-3), 2.76 (2H, m, H-4), 1.81 (2H, m, H-1-), 1.59 (2H, m, H-2-), 1.46 (2H, m, H-3-), 1.37 (3H, d, *J* = 6.0 Hz, H-5-); ESI-MS *m*/*z* 774.3 [M + K]+.

(*S*)-MTPA ester of **3**: 1H NMR (CDCl3, 600 MHz): *δ*H 6.88 (1H, s, H-6), 5.14 (1H, m, H-4-), 4.21 (1H, m, H-3), 2.43 (2H, m, H-4), 1.72 (2H, m, H-1-), 1.52 (2H, m, H-2-), 1.43 (2H, m, H-3-), 1.35 (3H, d, *J* = 9.4 Hz, H-5-); ESI-MS *m*/*z* 766.6 [M + Na]+.

(*R*)-MTPA ester of **3**: 1H NMR (CDCl3, 600 MHz): *δ*H 6.86 (1H, s, H-6), 5.13 (1H, m, H-4-), 4.07 (1H, m, H-3), 2.33 (2H, m, H-4), 1.65 (2H, m, H-1-), 1.51 (2H, m, H-2-), 1.42 (2H, m, H-3-), 1.28 (3H, d, *J* = 9.4 Hz, H-5-); ESI-MS *m*/*z* 766.0 [M + Na]+.
