*3.5. Isolation and Structural Elucidation*

An amount of 150 g from aqueous methanol leaf extract (CLL; see Section 3.1) was fractionated using a polyamide column (Figure S69). Elution started with distilled H2O followed by H2O/MeOH, with gradual increase until reaching pure MeOH. The obtained fractions from the column (500 mL each) were examined using PC and TLC and observed under UV light. Similar fractions were pooled together, according to their TLC and PC profiles, to furnish 9 major fractions (A~I). Fraction B was the selected fraction for further purification based on TLC and PC detection. Fraction B (100% H2O, 40 g) was subjected to column chromatography (CC) on Sephadex LH-20 with aqueous MeOH for elution (30–100%). Similar fractions were pooled together, according to their TLC profiles, to furnish 7 fractions, B-1~B-7.

Fraction B-4 (30% MeOH, 700 mg) was subjected to reversed-phase flash column chromatography using a Buchi MPLC eluted with a gradient solvent mixture of MeOH/H2O (*v*/*v*, 4:6→ 5:5→ 6:4→ 7:3→8:2→9:1, each 400 mL, and flushed with 600 mL 100% MeOH). Similar fractions were pooled together, according to their TLC profiles, to afford 15 fractions, B-4-1~B-4-15. Fraction B-4-4 (*v*/*v*, 4:6 MeOH/H2O, 42 mg) was repeatedly purified with an n-PTLC to yield compound 5 (4 mg). Further, fraction B-4-11 (*v*/*v*, 5:5 MeOH/H2O, 150 mg) was repeatedly purified with an n-PTLC to yield compound 6 (3 mg). In addition, fraction B-4-13 (*v*/*v*, 5:5 MeOH/H2O, 25 mg) was repeatedly purified with an n-PTLC to yield compounds 7 and 8 (7 and 6 mg, respectively) (Figure S69).

Fraction B-6 (50% MeOH, 5.5 gm) was subjected to chromatographic separation using Sephadex LH-20 column eluted with *n*-butanol/H2O (1:1), to afford fractions B-6-1~B-6-9. Fraction B-6-6 (700 mg) was subjected to reversed-phase flash column chromatography using a Buchi MPLC and eluted with a gradient solvent mixture of MeOH/H2O (*v*/*v*, 20:80–100:0, each 400 mL) MPLC to afford 17 subfractions B-6-6-1~B-6-6-17. Subfraction B-6-6-3 (*v*/*v*, 4:6 MeOH/H2O, 16 mg) was repeatedly purified with an n-PTLC to yield compound 1 (7 mg). Further, subfraction B-6-6-12 (*v*/*v*, 6:4 MeOH/H2O, 40 mg) was repeatedly purified with an n-PTLC to afford compounds 9, 10 and 11 (6, 8.5 and 10 mg, respectively) (Figure S69).

Similarly, Fraction B-6-7 (2.2 g) was fractionated on a Sephadex LH-20 column, using *n*-butanol/H2O (1:1) to afford fractions B-6-7-1~B-6-7-3. Thereafter, subfraction B-6-7-3 (76 mg) was separated by reversed-phase flash column chromatography using a Buchi MPLC and eluted with a gradient solvent mixture of MeOH/H2O (*v*/*v*, 40:60–100:0, each 400 mL and flushed with 1000 mL 100% MeOH) to yield compound 2 (*v*/*v*, 5:5 MeOH/H2O, 7.4 mg) (Figure S69).

Fraction B-7 (50% MeOH, 1.14 g) was subjected to Sephadex eluted with butanol/H2O (1:1; *v*/*v*) to furnish fractions B-7-1~B-7-7. Moreover, the fractionation of fraction B-7-5 (146 mg) on reversed-phase flash column chromatography using a Buchi MPLC and eluted with a gradient solvent mixture of MeOH/H2O (*v*/*v*, 40:60 to 100:0, each 400 mL), which resulted in pure compounds 3, 4, and 12 (8, 4, and 5 mg, respectively).

Compound **<sup>1</sup>**: Yellowish amorphous powder (MeOH); [α]D25 −2.72 (c 0. 0044, MeOH); UV (MeOH) λmax nm (log ε) 225 (2.39), 271 (2.43) and 333 (2.49) (Figure S70); IR (FTIR): ν = 3431, 2360, 1623 cm1 (Figure S71); Rt from HPLC 14.76 min; HR-ESI-MS detected at *m*/*z* 561.1614 [M-H]<sup>−</sup> (calculated at *<sup>m</sup>*/*<sup>z</sup>* 561.16137, C27H29O13−, error −0.1 ppm); 1H (600 MHz) and 13C (150 MHz) NMR data in CD3OD, see Table 2.

Compound **<sup>2</sup>**: Yellowish amorphous powder (MeOH); [α]D<sup>25</sup> −2.2 (c 0. 005, MeOH); UV (MeOH) λmax nm (log ε) 226 (2.23), 272 (2.25) and 329 (2.37) (Figure S70); Rt from HPLC 14.59 min; HRESIMS *m/z* 577.1600 [M-H]<sup>−</sup> (calculated C27H29O14−, error 6.53 ppm); 1H (600 MHz) and 13C (150 MHz) NMR data in CD3OD, see Table 2.

Compound **3**: Yellowish amorphous powder (MeOH); [α]D25 15.0289 (c 0. 00519, MeOH); UV (MeOH) λmax nm (log ε) 269 (1.33) and 335 (1.3) (Figure S70); Rt from HPLC 12.44 min; HRESIMS *m*/*z* 431.0986 [M-H]<sup>−</sup> (calculated C21H19O10−, error 0.62 ppm); 1H (600 MHz) and 13C (150 MHz) NMR data in CD3OD, see Table 2.

Compound **4**: Yellowish amorphous powder (MeOH); [α]D25 1.689 (c 0. 00296, MeOH); UV (MeOH) λmax nm (log ε) 269 (2.73) and 336 (2.75) (Figure S70); Rt from HPLC 15.42 min; HRESIMS *m*/*z* 561.1661 [M-H]<sup>−</sup> (calculated C27H29O13−, error 8.03 ppm); 1H (600 MHz) and 13C (150 MHz) NMR data in CD3OD, see Table 2.

Compound **5**: Yellowish amorphous powder (MeOH); [α]D<sup>25</sup> +8.9 (c 0.003, MeOH); UV (MeOH) λmax nm (log ε) 232 (1.92) and 286 (1.94) (Figure S70); Rt from HPLC 12.88 min; HRESIMS *m*/*z* 713.2272 [M-H]<sup>−</sup> (calculated C32H41O18−, error 3.69 ppm); 1H (600 MHz) and 13C (150 MHz) NMR data in CD3OD, see Table 3.

Compound **<sup>6</sup>**: Yellowish amorphous powder (MeOH); [α]D25 −20.69 (c 0.0003, MeOH); UV (MeOH) λmax nm (log ε) 228 (0.63) and 284 (0.54) (Figure S70); Rt from HPLC 14.37 min; HRESIMS *m*/*z* 697.2350 [M-H]<sup>−</sup> (calculated C32 H41O17−, error 0.06 ppm); 1H (600 MHz) and 13C (150 MHz) NMR data in CD3OD, see Table 3.

Compound **<sup>7</sup>**: Yellowish amorphous powder (MeOH); [α]D25 −66.41 (c 0.003, MeOH); UV (MeOH) λmax nm (log ε) 231 (2.53) and 284 (2.58) (Figure S70); Rt from HPLC 18.15 min; HRESIMS *m*/*z* 973.3340 [M-H]<sup>−</sup> (calculated C47 H57O22−, error 1.1 ppm); 1H (600 MHz) and 13C (150 MHz) NMR data in CD3OD, see Table 3.

Compound **<sup>8</sup>**: Yellowish amorphous powder (MeOH); [α]D25 −40.39 (c 0.003, MeOH); UV (MeOH) λmax nm (log ε) 230 (1.60) and 285 (1.65) (Figure S70); IR (FTIR): ν = 3433, 2921, 1616, 1516, 1449, 1382, 1222, 1173, 1073 cm<sup>1</sup> (Figure S71); Rt from HPLC 18.14 min; HRESIMS detected at *m*/*z* 1015.3460 [M-H]− (calculated at *m*/*z* 1015.34526, C49H59O23−, error −0.7 ppm); 1H (600 MHz) and 13C (150 MHz) NMR data in CD3OD, see Table 3.

Compound **<sup>9</sup>**: Yellowish amorphous powder (MeOH); [α]D25 −31.379 (c 0. 0015, MeOH); UV (MeOH) λmax nm (log ε) 232 (1.99) and 290 (2.03) (Figure S70); Rt from HPLC 18.10 min; HRESIMS *m*/*z* 827.2768 [M-H]<sup>−</sup> (calculated C41H47O18−, error 0.78 ppm); 1H (600 MHz) and 13C (150 MHz) NMR data in CD3OD, see Table 3.

Compound **<sup>10</sup>**: Yellowish amorphous powder (MeOH); [α]D25 −102.778 (c 0. 0014, MeOH); UV (MeOH) λmax nm (log ε) 230 (1.94), 290 (1.99) and 310 (2.05) (Figure S70); Rt from HPLC 17.50 min; HRESIMS *m*/*z* 989.3289 [M-H]− (calculated C47H57O23−, error 0.67 ppm); 1H (600 MHz) and 13C (150 MHz) NMR data in CD3OD, see Table 4.

Compound **<sup>11</sup>**: Yellowish amorphous powder (MeOH); [α]D25 −95.42 (c 0. 0024, MeOH); UV (MeOH) λmax nm (log ε) 226 (1.27) and 286 (1.26) (Figure S70); IR (FTIR): ν = 3433, 2921, 1616, 1516, 1449, 1382, 1222, 1173, 1073 cm1 (Figure S71); Rt from HPLC

17.60 min; HRESIMS detected at *m*/*z* 1031.3389 [M-H]− (calculated at *m*/*z* 1031.34018, C49H59O24−, error + 1.2 ppm); 1H (600 MHz) and 13C (150 MHz) NMR data in CD3OD, see Table 4.

Compound **<sup>12</sup>**: Yellowish amorphous powder (MeOH); [α]D25 −112.25 (c 0. 004, MeOH); λmax nm (log ε) 226 (2.17), 290 (2.21) and 310 (2.19) (Figure S70); Rt from HPLC 16.94 min; HRESIMS *m*/*z* 843.2782 [M-H]<sup>−</sup> (calculated C41H47 O19−, error 7.27 ppm); 1H (600 MHz) and 13C (150 MHz) NMR data in CD3OD, see Table 4.
