*3.4. Physical and Chemical Data*

Psegynamide A (**1**): white amorphous powder; [*α*] 20D + 30.2 (*c* 0.2, MeOH); UV (DAD) λmax 218 nm, 283 nm; 1H and 13C NMR (DMSO-*d*6), see Table 1; HREIMS *m/z* 550.3025 [M + H]+ (cacld for C30H40N5O5, 550.3024).

Psegynamide B (**2**): white amorphous powder; [*α*] 20D + 23.8 (*c* 0.3, MeOH); UV (DAD) λmax 217 nm, 283 nm; 1H and 13C NMR (DMSO-*d*6), see Table 1; HREIMS *m/z* 564.3172 [M + H]+ (cacld for C31H42N5O5, 564.3180).

Psegynamide C (**3**): white amorphous powder; [*α*] 20D + 25.3 (*c* 0.3, MeOH); UV (DAD) λmax 217 nm, 282 nm; 1H and 13C NMR (DMSO-*d*6), see Table 1; HREIMS *m/z* 566.2977 [M + H]+ (cacld for C30H40N5O6, 566.2973).

Psegynamide D (**4**): white amorphous powder; [*α*] 20D − 14.7 (*<sup>c</sup>* 0.3, MeOH); UV (DAD) λmax 217 nm, 282 nm; 1H and 13C NMR (DMSO-*d*6), see Table 2; HREIMS *m/z* 562.3032 [M + H]+ (cacld for C31H40N5O5, 562.3024).

Psegynamide E (**5**): white amorphous powder; [*α*] 20D − 17.8 (*<sup>c</sup>* 0.2, MeOH); UV (DAD) λmax 216 nm, 282 nm; 1H and 13C NMR (DMSO-*d*6), see Table 2; HREIMS *m/z* 576.3186 [M + H]+(cacld for C32H42N5O5, 576.3180).

Psegynamide F (**6**): white amorphous powder; [*α*] 20D − 20.3 (*<sup>c</sup>* 0.2, MeOH); UV (DAD) λmax 216 nm, 283 nm; 1H and 13C NMR (DMSO-*d*6), see Table 2; HREIMS *m/z* 592.3133 [M + H]+ (cacld for C32H42N5O6, 592.3130).

#### *3.5. Advanced Marfey's Analysis of Acid Hydrolytic for Val, Phe, Tyr*

Compounds **1**–**6** (1.0 mg each) were reacted with 6 M HCl (1.5 mL) at 110 ◦C for 12 h; the hydrolysates were concentrated to dryness. The hydrolysates and standard amino acids (150 μM) were then successively treated with water (300 μL), FDAA (10 mg/mL solution in acetone, 100 μL), acetone (300 μL), and NaHCO3 (1 M, 150 μL) at 45 ◦C water bath heating for 2.0 h. Then, the reaction was stopped with HCl (2 M, 75 μL) prior to HPLC analysis. Amino acid standards were similarly derivatized with FDAA. The resulting FDAA derivatives of compounds **1**–**6**, *L*- and *D*-Val, *L*- and *D*- Phe, *L*- and *D*- Tyr were analyzed by HPLC eluted with a linear gradient of MeOH (A) and 0.10% aqueous TFA (B) from 40% to 100% in an over 45 min with UV detection at 340 nm.

#### *3.6. Modified Marfey's Analysis of Alkaline Hydrolytic for Trp*

Considering that Trp FDAA derivatives were not detected in the resulting FDAA derivatives of compounds **1**–**3**, it might result from that Trp amino acid was hydrolytic and destroyed in strong hydrochloric acid. Therefore, Marfey's alkaline hydrolytic method was considered to determine the absolute configuration of Trp residue. Through continuous attempts, the alkaline hydrolytic condition of 5 M LiOH at 110 ◦C for 16 h was finally adopted, and the absolute configuration of Trp was determined as *L*.
