*3.6. Structural Elucidation*

All the compounds were submitted to one-dimensional and two-dimensional NMR analysis, high resolution mass spectrometry, and, when appropriate, to crystallography.

Peniciphenalenin D (**1**): Red amorphous solid (31 mg); [α]D25: +119.70◦ (*c* 0.1, MeOH); UV (MeOH) λmax (log ε) 217 (3.83), 279 (3.85), 369 (2.91), 515 (2.90) nm; 1H and 13C NMR data, see Supplementary Information; HRESIMS *m*/*z* 317.1005 [M + H]<sup>+</sup> (calcd. for C17H17O6, 317.1025).

Isoconiolactone (**2**) + Coniolactone (**3**): Orange amorphous powder (40 mg); UV (MeOH) λmax (log ε) 220 (3.52), 254 (2.54), 346 (1.45) nm; 1H and 13C NMR data, Table 1; Table 2; HRESIMS *m*/*z* 301.1067 [M + H]<sup>+</sup> (calcd. for C17H17O5, 301.1076)

(−)-Peniciphenalenin F (**4**): Yellowish amorphous powder (15 mg); [α]D: −36.10◦ (c 0.1, MeOH); UV (MeOH) λmax (log ε) 221 (4.22), 274 (4.21), 357 (3.51), 393 (3.33) nm; 1H and 13C NMR data, Table 1; Table 2; HRESIMS *m*/*z* 301.1053 [M + H]<sup>+</sup> (calcd. for C17H17O5, 301.1049)

(+)-8-Hydroxyscleroderolide (**5**): Pale yellowish amorphous powder (36 mg); [α]D: +65.01◦ (c 0.1, MeOH); UV (MeOH) λmax (log ε) 244 (3.56), 448 (1.71) nm; 1H and 13C NMR data, Table 1; Table 2; HRESIMS *m*/*z* 345.0967 [M + H]<sup>+</sup> (calcd. for C18H17O7, 345.0974).

(−)-7,8-Dihydro-3,6-dihydroxy-1,7,7,8-tetramethyl-5H-furo-[2- ,3- :5,6]naphtho[1,8-bc]furan-5-one (**6**): Yellowish amorphous powder (5 mg); [α]D: −36.80◦ (c 0.1, MeOD); UV (MeOH) λmax (log ε) 226 (1.22), 263 (3.65), 359 (3.52) nm; 1H and 13C NMR data, see Supplementary Information; HRESIMS *m*/*z* 301.1064 [M + H]<sup>+</sup> (calcd. for C17H17O5, 301.1076).

(+)-Scleroderolide (**7**): Yellow powder (57 mg); [α]D: +73.0◦ (c 0.1, MeOD); UV (MeOH) λmax (log ε) 226 (3.88), 250 (2.87), 294 (1.22), 439 (2.12) nm; 1H and 13C NMR data, see Supplementary Information; HRESIMS *m*/*z* 329.1033 [M + H]<sup>+</sup> (calcd. for C18H17O6, 329.1039).

(+)-8-Hydroxysclerodin (**8**): Pale yellow crystal (38 mg); [α]D: +66.01◦ (c 0.1, MeOH); UV (MeOH) λmax (log ε) 223 (3.38), 308 (1.14), 358 (2.52) nm; 1H and 13C NMR data, Table 1; Table 2; HRESIMS *m*/*z* 345.0960 [M + H]<sup>+</sup> (calcd. for C18H17O7, 345.0961).

Coniosclerodin (**9**): Pale yellow powder (8 mg); UV (MeOH) λmax (log ε) 250 (4.12), 289 (1.14), 351 (3.52) nm; 1H and 13C NMR data, see Supplementary Information; HRESIMS *m*/*z* 329.1001 [M + H]<sup>+</sup> (calcd. for C18H17O6, 329.1025).

(+)-Sclerodin (**10**): Yellowish powder (7 mg); [α]D: +20.01◦ (c 0.10, CH2Cl2); UV (MeOH) λmax (log ε) 216 (3.25), 256 (4.13), 295 (1.24), 359 (3.98) nm; 1H and 13C NMR data, see Supplementary Information; HRESIMS *m*/*z* 329.1015 [M + H]<sup>+</sup> (calcd. for C18H17O6, 329.1025).
