Supporting Information Two Enantiomeric Pairs of Meroterpenoids from Rhododendron capitatum Hai-Bing Liao, Chun Lei, Li-Xin Gao, Jing-Ya Li, Jia Li, and Ai-Jun Hou*, Department of Pharmacognosy, School of Pharmacy, Fudan University, 826 Zhang Heng Road, Shanghai 201203, P. R. China National Center for Drug Screening, State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 189 Guo Shou Jing Road, Shanghai 201203, P. R. China ajhou@shmu.edu.cn S1
Table of Contents Table S1. 1 H and 13 C NMR spectroscopic data of rhodonoid A (1), ( )-rhodonoid A (1a), and ( )-rhodonoid A (1b) in CDCl 3 Table S2. 1 H and 13 C NMR spectroscopic data of rhodonoid B (2), ( )-rhodonoid B (2a), and ( )-rhodonoid B (2b) in CDCl 3 Figure S1. Chiral HPLC chromatogram of rhodonoid A (1) Figure S2. Chiral HPLC chromatogram of rhodonoid B (2) Experimental section General experimental procedures Plant material Extraction and isolation Physical constants and spectroscopic data of 1, 1a, 1b, 2, 2a, and 2b X-ray crystallographic data for rhodonoid A (1) X-ray crystallographic data for ( )-rhodonoid A (1a) X-ray crystallographic data for ( )-rhodonoid B (2a) Bioassay MS, NMR, IR, [ ] D, and ECD spectra of 1, 1a, 1b, 2, 2a, and 2b For rhodonoid A (1) Figure S3. Negative ESIMS spectrum of rhodonoid A (1) Figure S4. Positive ESIMS spectrum of rhodonoid A (1) Figure S5. Positive HR-ESIMS spectrum of rhodonoid A (1) Figure S6 7. 1 H NMR spectrum of rhodonoid A (1) Figure S8. 13 C NMR and DEPT spectra of rhodonoid A (1) Figure S9 10. HSQC spectrum of rhodonoid A (1) Figure S11 13. HMBC spectrum of rhodonoid A (1) Figure S14. Specific rotation of rhodonoid A (1) S2
For ( )-rhodonoid A (1a) Figure S15. Specific rotation of ( )-rhodonoid A (1a) Figure S16. Positive HR-ESIMS spectrum of ( )-rhodonoid A (1a) Figure S17. IR spectrum of ( )-rhodonoid A (1a) Figure S18. 1 H NMR spectrum of ( )-rhodonoid A (1a) Figure S19. 13 C NMR and DEPT spectra of ( )-rhodonoid A (1a) Figure S20 21. ROESY spectrum of ( )-rhodonoid A (1a) For ( )-rhodonoid A (1b) Figure S22. Specific rotation of ( )-rhodonoid A (1b) Figure S23. Positive HR-ESIMS spectrum of ( )-rhodonoid A (1b) Figure S24. IR spectrum of ( )-rhodonoid A (1b) Figure S25. 1 H NMR spectrum of ( )-rhodonoid A (1b) Figure S26. 13 C NMR and DEPT spectra of ( )-rhodonoid A (1b) For rhodonoid B (2) Figure S27. Negative ESIMS spectrum of rhodonoid B (2) Figure S28. Positive ESIMS spectrum of rhodonoid B (2) Figure S29. Positive HR-ESIMS spectrum of rhodonoid B (2) Figure S30 31. 1 H NMR spectrum of rhodonoid B (2) Figure S32. 13 C NMR and DEPT spectra of rhodonoid B (2) Figure S33 34. HSQC spectrum of rhodonoid B (2) Figure S35. Specific rotation of rhodonoid B (2) For ( )-rhodonoid B (2a) Figure S36. Specific rotation of ( )-rhodonoid B (2a) Figure S37. Positive HR-ESIMS spectrum of ( )-rhodonoid B (2a) Figure S38. IR spectrum of ( )-rhodonoid B (2a) Figure S39. 1 H NMR spectrum of ( )-rhodonoid B (2a) Figure S40. 13 C NMR and DEPT spectra of ( )-rhodonoid B (2a) S3
For ( )-rhodonoid B (2b) Figure S41. Specific rotation of ( )-rhodonoid B (2b) Figure S42. Positive HR-ESIMS spectrum of ( )-rhodonoid B (2b) Figure S43. IR spectrum of ( )-rhodonoid B (2b) Figure S44. 1 H NMR spectrum of ( )-rhodonoid B (2b) Figure S45. 13 C NMR and DEPT spectra of ( )-rhodonoid B (2b) Figure S46 47. HMBC spectrum of ( )-rhodonoid B (2b) Figure S48. ROESY spectrum of ( )-rhodonoid B (2b) S4
Table S1. 1 H and 13 C NMR spectroscopic data of rhodonoid A (1), ( )-rhodonoid A (1a), and ( )-rhodonoid A (1b) in CDCl 3 1 a 1a b 1b b no. (multi, J in Hz) C (multi, J in Hz) C (multi, J in Hz) C 2 73.6 73.6 73.6 3 2.59 (d, 9.5) 51.2 2.59 (d, 9.6) 51.2 2.59 (d, 9.6) 51.2 4 3.75 (td, 9.5, 7.0) 21.9 3.75 (td, 9.6, 7.2) 21.9 3.74 (td, 9.6, 7.2) 21.9 4a 112.6 112.6 112.6 5 154.3 154.3 154.3 6 6.33 (br s) 112.3 6.34 (br s) 112.3 6.34 (br s) 112.3 7 137.6 137.6 137.7 8 6.21 (br s) 109.3 6.21 (br s) 109.3 6.21 (br s) 109.3 8a 152.6 152.6 152.6 9 2.03 (ddd, 14.0, 11.0, 7.0) 2.33 (ddd, 14.0, 7.0, 3.5) c 34.2 2.03 (ddd, 14.0, 11.0, 6.6) 2.33 (ddd, 14.0, 7.0, 3.6) c 34.2 2.03 (ddd, 14.0, 11.0, 7.0) 2.33 (ddd, 14.0, 7.0, 3.6) c 34.2 10 2.78 (ddd, 18.0, 11.0, 7.0) 33.7 2.78 (ddd, 18.0, 11.0, 7.0) 33.7 2.78 (ddd, 18.0, 11.0, 7.0) 33.7 2.42 (ddd, 18.0, 7.0, 3.5) 2.42 (ddd, 18.0, 6.6, 3.6) 2.42 (ddd, 18.0, 6.6, 3.6) 11 215.7 215.6 215.5 12 43.9 43.9 43.9 13 2.18 (dd, 12.0, 7.0) 2.36 (br dd, 12.0, 9.5) c 39.0 2.18 (dd, 12.0, 7.2) 2.36 (br dd, 12.0, 9.6) c 39.0 2.18 (dd, 12.0, 7.2) 2.36 (br dd, 12.0, 9.6) c 39.0 14 1.44 (s) 25.0 1.44 (s) 25.0 1.44 (s) 25.0 15 1.15 (s) 25.6 1.16 (s) 25.6 1.16 (s) 25.6 16 2.21 (s) 21.4 2.22 (s) 21.4 2.22 (s) 21.4 5-OH 4.78 (br s) 4.67 (br s) 4.57 (br s) a Data were measured at 500 MHz ( 1 H) and 125 MHz ( 13 C). b Data were measured at 400 MHz ( 1 H) and 150 MHz ( 13 C). c Signals overlapped within the same column. S5
Table S2. 1 H and 13 C NMR spectroscopic data of rhodonoid B (2), ( )-rhodonoid B (2a), and ( )-rhodonoid B (2b) in CDCl 3 2 a 2a b 2b b no. (multi, J in Hz) C (multi, J in Hz) C (multi, J in Hz) C 2 83.9 83.9 83.9 3 2.59 (dd, 9.0, 8.0) c 39.1 2.60 (dd, 10.4, 8.0) c 39.1 2.59 (dd, 10.0, 8.0) c 39.1 4 3.17 (d, 9.0) 36.6 3.17 (d, 10.4) 36.5 3.17 (d, 10.0) 36.5 4a 109.6 109.6 109.7 5 154.2 154.1 154.1 6 6.25 (br s) 109.6 6.25 (br s) 109.6 6.25 (br s) 109.7 7 137.8 137.8 137.8 8 6.33 (br s) 111.9 6.33 (br s) 111.9 6.33 (br s) 112.0 8a 154.6 154.5 154.6 9 1.94 (m) 39.5 1.94 (m) 39.5 1.94 (m) 39.5 1.58 (m) 1.58 (m) 1.58 (m) 10 1.72 (m) 26.9 1.72 (m) 26.9 1.72 (m) 26.8 1.63 (m) 1.63 (m) 1.63 (m) 11 2.62 (m) c 47.0 2.62 (m) c 47.0 2.62 (m) c 47.0 12 41.7 41.7 41.7 13 2.41 (d, 18.6) 45.6 2.41 (d, 18.4) 45.6 2.39 (d, 18.0) 45.6 2.49 (d, 18.6) 2.50 (d, 18.4) 2.49 (d, 18.0) 14 201.6 201.6 201.5 15 5.89 (br s) 125.0 5.89 (br s) 124.9 5.88 (br s) 124.9 16 154.4 154.4 154.4 17 1.78 (br s) 27.7 1.78 (br s) 27.7 1.78 (br s) 27.7 18 2.04 (br s) 20.7 2.04 (br s) 20.7 2.04 (br s) 20.7 19 1.53 (s) 30.5 1.53 (s) 30.5 1.53 (s) 30.5 20 1.32 (s) 26.4 1.32 (s) 26.4 1.31 (s) 26.3 21 2.22 (s) 21.4 2.22 (s) 21.4 2.23 (s) 21.4 5-OH 5.42 (br s) 5.32 (br s) 5.15 (br s) a Data were measured at 600 MHz ( 1 H) and 150 MHz ( 13 C). b Data were measured at 400 MHz ( 1 H) and 150 MHz ( 13 C). c Signals overlapped within the same column. S6
Figure S1. Chiral HPLC chromatogram of rhodonoid A (1) Compound Retention Time (min) Analysis results Height ( V) Area ( V*S) Area% 1b 36.069 244058 9481242 16.05233 1a 43.582 768990 49583339 83.94767 Column: Daicel chiralpak AD-H (250 20 mm, 5 m) Mobile phase: n-hexane/isopropanol (85 15) Flow rate: 4 ml/min Wavelength: 210 nm S7
Figure S2. Chiral HPLC chromatogram of rhodonoid B (2) Compound Retention Time (min) Analysis results Height ( V) Area ( V*S) Area% 2a 36.384 998523 108268483 69.04348 2b 57.510 993794 48543537 30.95652 Column: Daicel chiralpak AD-H (250 20 mm, 5 m) Mobile phase: n-hexane/isopropanol (95 5) Flow rate: 4 ml/min Wavelength: 210 nm S8
Experimental Section General experimental procedures Melting points were measured on a SGM X-4 apparatus (Shanghai Precision & Scientific Instrument Co., Ltd., China). Optical rotations were recorded on a Perkin-Elmer 341 polarimeter (Wellesley, MA, USA). UV and ECD spectra were recorded on a JASCO J-810 instrument (JASCO Co., Japan). IR spectra were recorded on a Nicolet 6700 FT-IR spectrometer (Thermo Fisher Scientific, USA). NMR spectra were acquired on Bruker AM-400, AM-500 or AM-600 NMR spectrometers (Bruker Biospin, Rheinstetten, Germany) using CDCl 3 as solvent. Chemical shifts were reported with respect to CDCl 3 ( H 7.26 and C 77.16). ESIMS and HRESIMS were obtained on a Bruker Daltonics Esquire 3000 plus LC-MS (Bruker Daltonics, Bremen, Germany) and a Waters-Micromass Q-TOF Ultima Global mass spectrometer (Milford, MA, USA), respectively. X-ray crystallographic analyses were performed on a Bruker APEX-II CCD detector (Bruker Biospin, Rheinstetten, Germany) employing graphite-monochromated Cu K radiation ( = 1.54178 Å). D101 macroporous resin (Shanghai Hualing Resin Co., Ltd., China), silica gel (200 300 mesh, Qingdao Haiyang Chemical Co., Ltd., China), C 18 reversed-phase (RP-18) silica gel (150 200 mesh, Merck, Germany), and MCI gel CHP-20P (75 150 m, Mitsubishi Chemical Co., Tokyo, Japan) were used for column chromatography, and precoated silica gel GF254 plates (Qingdao Haiyang Chemical Co., Ltd., China) were used for TLC. Semi-preparative HPLC was performed on a Waters 515 pump equipped with a Waters 2487 UV detector (Waters, Milford, MA, USA ) and a YMC-Pack ODS-A column (250 10 mm, 5 m, YMC Co., Kyoto, Japan). Daicel chiralpak AD-H column (250 20 mm, 5 m, Daicel Chiral Technologies (China) Co., Ltd.) was used to perform chiral separation on an Organizer LC 2050 (Tian Mei Co., Ltd., China). Plant material The aerial parts of Rhododendron capitatum were collected in Qinghai province, S9
People s Republic of China, in August 2012. The plant material was identified by Prof. Yanduo Tao, Northwest Institute of Plateau Biology, Chinese Academy of Sciences, and a voucher specimen (TCM 12-09-1 Hou) has been deposited at the Herbarium of the Department of Pharmacognosy, School of Pharmacy, Fudan University. Extraction and isolation The milled and air-dried aerial parts of R. capitatum (10 kg) were percolated with 95% EtOH at room temperature. The filtrate was evaporated under reduced pressure to give a crude extract (2 kg), which was suspended in H 2 O and extracted with EtOAc. The EtOAc-soluble fraction (1.5 kg) was subjected to column chromatography over D101 macroporous resin eluted with EtOH/H 2 O (from 1 9 to 9 1) to afford fractions A E. Fraction D (250 g) was separated by a MCI gel column eluted with MeOH/H 2 O (from 4 6 to 10 0) to give fractions D1 D8. Fraction D4 (25 g) was chromatographed on a silica gel column eluted with petroleum ether/me 2 CO (from 10 1 to 1 1) to yield fractions D4a D4d. Fraction D4b (2 g) was separated on a RP-18 silica gel column (MeOH/H 2 O, from 3 7 to 8 2) to yield fractions D4b1 D4b4. Fraction D4b2 was purified by semi-preparative HPLC (MeOH/H 2 O, 65 35, flow rate 3 ml/min) to give compound 1 (5.0 mg). Compound 2 (8.0 mg) was obtained from fraction D4b3 using semi-preparative HPLC (MeOH/H 2 O, 7 3, flow rate 3 ml/min). Compounds 1 and 2 were applied to chiral HPLC separation using n-hexane/isopropanol (85 15 for 1 and 95 5 for 2, flow rate 4 ml/min) as mobile phase to provide compounds 1a (3.5 mg), 1b (0.8 mg), 2a (3.2 mg), and 2b (1.2 mg). Physical constants and spectroscopic data of 1, 1a, 1b, 2, 2a, and 2b Rhodonoid A (1): colorless crystals (MeOH); [ ] 25 D 34.8 (c 0.05, MeOH); UV (MeOH) max (log ) 209 (4.25), 343 (3.29) nm; 1 H NMR and 13 C NMR data, see Table 1; positive ESIMS m/z 273.0 [M H] +, 567.0 [2M+Na] + ; negative ESIMS m/z 271.0 [M H], 543.1 [2M H] ; positive HRESIMS m/z 567.2720 [2M Na] (calcd for C 34 H 40 O 6 Na, 567.2723). ( )-Rhodonoid A (1a): colorless crystals (MeOH); mp 160 162 C; [ ] 20 D 39.0 (c 0.10, MeOH); UV (MeOH) max (log ) 209 (4.25), 343 (3.29) nm; ECD (MeOH) S10
max nm ( ) 206.0 ( 18.20), 239.0 (+1.93), 271.0 ( 0.18), 299.0 (+3.13); IR (KBr) ν max 3420, 3236, 2956, 2925, 2853, 1685, 1622, 1591, 1463, 1421, 1326, 1284, 1188, 1133, 1102, 1068, 1054, 991, 974, 866, 829 cm 1 ; 1 H NMR and 13 C NMR data, see Table S1; positive HRESIMS m/z 567.2722 [2M+Na] + (calcd for C 34 H 40 O 6 Na, 567.2723). ( )-Rhodonoid A (1b): white amorphous powder (MeOH); [ ] 20 D +38.0 (c 0.10, MeOH); UV (MeOH) max (log ) 209 (4.25), 343 (3.29) nm; ECD (MeOH) max nm ( ) 205.5 (+18.60), 239.0 ( 0.82), 272.0 (+0.86), 298.5 ( 2.37); IR (KBr) ν max 3422, 3251, 2954, 2923, 2854, 1687, 1624, 1591, 1456, 1422, 1381, 1285, 1209, 1188, 1132, 1102, 1054, 990, 974, 866, 830 cm 1 ; 1 H NMR and 13 C NMR data, see Table S1; positive HRESIMS m/z 567.2712 [2M+Na] + (calcd for C 34 H 40 O 6 Na, 567.2723). Rhodonoid B (2): white amorphous powder (MeOH); [ ] 25 D 37.2 (c 0.07, MeOH); UV (MeOH) max (log ) 211 (4.40) nm; 1 H NMR and 13 C NMR data, see Table 1; positive ESIMS m/z 341.2 [M+H] +, 703.3 [2M+Na] + ; negative ESIMS m/z 339.4 [M H], 679.6 [2M H] ; positive HRESIMS m/z 703.3976 [2M Na] (calcd for C 44 H 56 O 6 Na, 703.3975). ( )-Rhodonoid B (2a): colorless crystals (MeOH); mp 148 149 C; [ ] 20 D 39.0 (c 0.10, MeOH); UV (MeOH) max (log ) 211 (4.40) nm; ECD (MeOH) max nm ( ) 211.5 (+2.56), 249.5 ( 0.87), 276.0 ( 0.82); IR (KBr) ν max 3451, 2968, 2943, 2928, 2866, 1673, 1609, 1584, 1513, 1444, 1417, 1369, 1344, 1326, 1223, 1211, 1171, 1146, 1076, 1056, 999, 907, 828 cm 1 ; 1 H NMR and 13 C NMR data, see Table S2; positive HRESIMS m/z 703.3976 [2M+Na] + (calcd for C 44 H 56 O 6 Na, 703.3975). ( )-Rhodonoid B (2b): white amorphous powder (MeOH); [ ] 20 D +42.0 (c 0.10, MeOH); UV (MeOH) max (log ) 211 (4.40) nm; ECD (MeOH) max nm ( ) 212.0 ( 1.90), 252.0 (+0.88), 279.5 (+0.81); IR (KBr) ν max 3451, 2959, 2927, 2854, 1673, 1609, 1584, 1513, 1444, 1370, 1327, 1264, 1223, 1171, 1152, 1100, 1089, 1056, 999, 907, 828 cm 1 ; 1 H NMR and 13 C NMR data, see Table S2; positive HRESIMS m/z 703.3986 [2M+Na] + (calcd for C 44 H 56 O 6 Na, 703.3975). S11
X-ray crystallographic data for rhodonoid A (1) Empirical formula C 17 H 20 O 3 Formula weight 272.33 Temperature 296(2) K Wavelength 1.54178 Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = 8.05390(10) Å, = 102.8620(10) b = 9.08260(10) Å, = 97.0710(10) c = 9.91750(10) Å, = 96.3840(10) Volume 694.648(13) Å 3 Z 2 Calculated density 1.302 Mg/m 3 Absorption coefficient 0.706 mm -1 F(000) 292 Crystal size 0.211 x 0.154 x 0.112 mm 3 Theta range for data collection 5.05 to 65.96 Index ranges -9<=h<=9, -10<=k<=9, -11<=l<=11 Reflections collected 4019 Independent reflections 2288 [R(int) = 0.0167] Completeness to theta = 65.96 94.3 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7532 and 0.6462 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 2288 / 0 / 186 Goodness-of-fit on F 2 1.063 Final R indices [I>2sigma(I)] R1 = 0.0426, wr2 = 0.1205 R indices (all data) R1 = 0.0441, wr2 = 0.1234 Extinction coefficient 0.0110(16) Largest diff. peak and hole 0.344 and -0.230 e.å -3 S12
X-ray crystallographic data for ( )-rhodonoid A (1a) Empirical formula C 17 H 20 O 3 Formula weight 272.33 Temperature 140(2) K Wavelength 1.54178 Å Crystal system Monoclinic Space group P21 Unit cell dimensions a = 8.30180(10) Å, = 90 b = 14.7835(2) Å, = 101.1260(10) c = 12.3636(2) Å, = 90 Volume 1488.86(4) Å 3 Z 4 Calculated density 1.215 Mg/m 3 Absorption coefficient 0.659 mm -1 F(000) 584 Crystal size 0.250 x 0.200 x 0.150 mm 3 Theta range for data collection 3.643 to 69.705 Index ranges -10<=h<=10, -17<=k<=16, -14<=l<=14 Reflections collected 10175 Independent reflections 4649 [R(int) = 0.0319] Completeness to theta = 67.679 98.8 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7533 and 0.5938 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4649 / 1 / 369 Goodness-of-fit on F 2 1.067 Final R indices [I>2sigma(I)] R1 = 0.0322, wr2 = 0.0895 R indices (all data) R1 = 0.0326, wr2 = 0.0900 Absolute structure parameter -0.03(8) Extinction coefficient n/a Largest diff. peak and hole 0.187 and -0.189 e.å -3 S13
X-ray crystallographic data for ( )-rhodonoid B (2a) Empirical formula C 22 H 28 O 3 Formula weight 340.44 Temperature 140(2) K Wavelength 1.54178 Å Crystal system Orthorhombic Space group P 21 21 21 Unit cell dimensions a = 11.37540(10) Å, = 90 b = 11.93599(10) Å, = 90 c = 14.18500(10) Å, = 90 Volume 1925.98(3) Å 3 Z 4 Calculated density 1.174 Mg/m 3 Absorption coefficient 0.604 mm -1 F(000) 736 Crystal size 0.200 x 0.080 x 0.030 mm 3 Theta range for data collection 4.842 to 69.573 Index ranges -10<=h<=12, -14<=k<=14, -17<=l<=17 Reflections collected 13941 Independent reflections 3464 [R(int) = 0.0435] Completeness to theta = 67.679 97.4 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7532 and 0.5980 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3464 / 0 / 232 Goodness-of-fit on F 2 1.041 Final R indices [I>2sigma(I)] R1 = 0.0351, wr2 = 0.0942 R indices (all data) R1 = 0.0363, wr2 = 0.0959 Absolute structure parameter 0.00(8) Extinction coefficient n/a Largest diff. peak and hole 0.170 and -0.168 e.å -3 Crystal data for compounds 1, 1a, and 2a were collected on a Bruker APEX-II CCD diffractometer employing graphite-monochromated Cu K radiation ( = 1.54178 Å). The structures were solved by direct methods using SHELXS-97 program and refined with full-matrix least-squares calculations on F 2 using SHELXL-97. Crystallographic data in this paper have been deposited at the Cambridge Crystallographic Data Center with the deposition numbers of CCDC 1419006 for 1, CCDC 1419007 for 1a, and CCDC 1419008 for 2a. Copies of the data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif. S14
Bioassay The bioassay procedures were the same as the reported previously. 1,2 A colorimetric assay to measure inhibition on PTP1B was performed in 96-well plates. The tested compounds were dissolved in DMSO with the initial concentration of 1 mg/ml, then serially diluted into the assay system and the final concentration of DMSO was 2%. Each sample was treated in three replicate wells. The assays were carried out in a final 100 µl mixture containing 50 mmol/l 3-[N-morpholino] propane-sulfonic acid (MOPs), ph 6.5, 2 mmol/l p-nitrophenyl phosphate (pnpp, Calbiochem), 30 nmol/l GST-PTP1B, and 2% DMSO. The enzymatic activities of PTP1B were determined by continuously monitoring the catalysis of pnpp on a SpectraMax 340 microplate reader (Molecular Devices, CA) at 405 nm for 3 min at 30 C. Oleanolic acid and DMSO were used as the positive control and negative control, respectively. The IC 50 was calculated with Prism 4 software (Graphpad, San Diego, CA). References 1. Shi, L.; Yu, H. P.; Zhou, Y. Y.; Du, J. Q.; Shen, Q.; Li, J. Y.; Li, J. Acta Pharmacol. Sin. 2008, 29, 278 284. 2. Wang, M.; Yu, B. W.; Yu, M. H.; Gao, L. X.; Li, J. Y.; Wang, H. Y.; Li, J.; Hou, A.J. Chem. Biodiversity 2015, 12, 937 945. S15
Figure S3. Negative ESIMS spectrum of rhodonoid A (1) S16
Figure S4. Positive ESIMS spectrum of rhodonoid A (1) S17
Figure S5. Positive HR-ESIMS spectrum of rhodonoid A (1) S18
Figure S6. 1 H NMR spectrum of rhodonoid A (1) S19
Figure S7. 1 H NMR spectrum of rhodonoid A (1) S20
Figure S8. 13 C NMR and DEPT spectra of rhodonoid A (1) S21
Figure S9. HSQC spectrum of rhodonoid A (1) S22
Figure S10. HSQC spectrum of rhodonoid A (1) S23
Figure S11. HMBC spectrum of rhodonoid A (1) S24
Figure S12. HMBC spectrum of rhodonoid A (1) S25
Figure S13. HMBC spectrum of rhodonoid A (1) S26
Figure S14. Specific rotation of rhodonoid A (1) S27
Figure S15. Specific rotation of ( )-rhodonoid A (1a) S28
Figure S16. Positive HR-ESIMS spectrum of ( )-rhodonoid A (1a) S29
Figure S17. IR spectrum of ( )-rhodonoid A (1a) S30
Figure S18. 1 H NMR spectrum of ( )-rhodonoid A (1a) S31
Figure S19. 13 C NMR and DEPT spectra of ( )-rhodonoid A (1a) S32
Figure S20. ROESY spectrum of ( )-rhodonoid A (1a) S33
Figure S21. ROESY spectrum of ( )-rhodonoid A (1a) S34
Figure S22. Specific rotation of ( )-rhodonoid A (1b) S35
Figure S23. Positive HR-ESIMS spectrum of ( )-rhodonoid A (1b) S36
Figure S24. IR spectrum of ( )-rhodonoid A (1b) S37
Figure S25. 1 H NMR spectrum of ( )-rhodonoid A (1b) S38
Figure S26. 13 C NMR and DEPT spectra of ( )-rhodonoid A (1b) S39
Figure S27. Negative ESIMS spectrum of rhodonoid B (2) S40
Figure S28. Positive ESIMS spectrum of rhodonoid B (2) S41
Figure S29. Positive HR-ESIMS spectrum of rhodonoid B (2) S42
Figure S30. 1 H NMR spectrum of rhodonoid B (2) S43
Figure S31. 1 H NMR spectrum of rhodonoid B (2) S44
Figure S32. 13 C NMR and DEPT spectra of rhodonoid B (2) S45
Figure S33. HSQC spectrum of rhodonoid B (2) S46
Figure S34. HSQC spectrum of rhodonoid B (2) S47
Figure S35. Specific rotation of rhodonoid B (2) S48
Figure S36. Specific rotation of ( )-rhodonoid B (2a) S49
Figure S37. Positive HR-ESIMS spectrum of ( )-rhodonoid B (2a) S50
Figure S38. IR spectrum of ( )-rhodonoid B (2a) S51
Figure S39. 1 H NMR spectrum of ( )-rhodonoid B (2a) S52
Figure S40. 13 C NMR and DEPT spectra of ( )-rhodonoid B (2a) S53
Figure S41. Specific rotation of ( )-rhodonoid B (2b) S54
Figure S42. Positive HR-ESIMS spectrum of ( )-rhodonoid B (2b) S55
Figure S43. IR spectrum of ( )-rhodonoid B (2b) S56
Figure S44. 1 H NMR spectrum of ( )-rhodonoid B (2b) S57
Figure S45. 13 C NMR and DEPT spectra of ( )-rhodonoid B (2b) S58
Figure S46. HMBC spectrum of ( )-rhodonoid B (2b) S59
Figure S47. HMBC spectrum of ( )-rhodonoid B (2b) S60
Figure S48. ROESY spectrum of ( )-rhodonoid B (2b) S61