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S1
Supporting Information
Bioactive Dibenzo-α-Pyrone Derivatives from the Endophytic Fungus
Rhizopycnis vagum Nitaf22
Daowan Lai,†,‡
Ali Wang,†,‡
Yuheng Cao,† Kaiyi Zhou,
† Ziling Mao,
† Xuejiao Dong,
†
Jin Tian,†, §
Dan Xu,† Jungui Dai,
Yu Peng,
║ Ligang Zhou,*
, † and Yang Liu *
,
† Key Laboratory of Plant Pathology, Ministry of Agriculture/Department of Plant
Pathology, College of Plant Protection, China Agricultural University, Beijing 100193,
China
§ National Centre for Plant Gene Research (Beijing), Institute of Genetics and
Developmental Biology, Chinese Academy of Sciences, Beijing 100101, China
State Key Laboratory of Bioactive Substance and Function of Natural Medicines,
Institute of Materia Medica, Chinese Academy of Medical Science & Peking Union
Medical College, Beijing 100050, China
║ Technical Centre of Hunan Tobacco Industry Co. Ltd., Changsha 410014, China
Institute of Food Science and Technology, Chinese Academy of Agricultural
Sciences/Key Laboratory of Agro-products Processing, Ministry of Agriculture,
Beijing 100193, China
‡ These authors contributed equally.
* Corresponding Authors
Tel.: +86 10 62731199 (L.Z.), +86 10 62815874 (Y.L.).
E-mail: [email protected] (L.Z), [email protected] (Y.L.).
S2
Table of Contents
1. Colony and Mycelia of Rhizopycnis vagum Nitaf22 ................................................................ S4
2. X-ray Crystallographic Data for Rhizopycnolide A (1) ......................................................... S4
Table S1. Crystal data and structure refinement for rhizopycnolide A (1) ............................. S4
Table S2. Fractional atomic coordinates (×104) and equivalent isotropic displacement
parameters (Å2×10
3) for rhizopycnolide A (1). ....................................................................... S5
Table S3. Anisotropic displacement parameters (Å2×10
3) for rhizopycnolide A (1). The
anisotropic displacement factor exponent takes the form: -2π2[h
2a*
2U11+...+2hka×b×U12] ... S6
Table S4. Bond lengths for rhizopycnolide A (1) ................................................................... S7
Table S5. Bond angles for rhizopycnolide A (1) ..................................................................... S7
Table S6. Torsion angles for rhizopycnolide A (1) ................................................................. S8
Table S7. Hydrogen atom coordinates (Å×104) and isotropic displacement parameters
(Å2×10
3) for rhizopycnolide A (1) ......................................................................................... S10
3. Computation Data for 1-3 ...................................................................................................... S11
Figure S1. The stable conformers of rhizopycnolide A (1) with populations greater than 1%
calculated from their relative free energies (ΔG). ................................................................. S11
Figure S2. The stable conformers of rhizopycnolide B (2) with populations greater than 1%
calculated from their relative free energies (ΔG). ................................................................. S11
Figure S3. The stable conformers of (1R, 4R)-3 and (1R, 4S)-3 with populations greater than
1% calculated from their relative free energies (ΔG). ........................................................... S12
Figure S4. The experimental ECD spectrum of 3 and the calculated ECD spectra of (1R,
4S)-3 and (1S, 4R)-3. ............................................................................................................. S12
4. (1D, 2D) NMR, IR, and HRESIMS Spectra of 1-6 ............................................................... S13
Figure S5. 1H NMR spectrum of 1 (DMSO-d6, 400 MHz) .................................................. S13
Figure S6. 13
C NMR spectrum of 1 (DMSO-d6, 100 MHz) ................................................. S13
Figure S7. HMQC spectrum of 1 (DMSO-d6)...................................................................... S14
Figure S8. HMBC spectrum of 1 (DMSO-d6) ...................................................................... S14
Figure S9. NOESY spectrum of 1 (DMSO-d6) .................................................................... S15
Figure S10. IR spectrum of 1 ............................................................................................... S15
Figure S11. HRESIMS spectrum of 1 .................................................................................. S16
Figure S12. 1H NMR spectrum of 2 (DMSO-d6, 400 MHz) ................................................ S16
Figure S13. 13
C NMR spectrum of 2 (DMSO-d6, 100 MHz) ............................................... S17
Figure S14. HMBC spectrum of 2 (DMSO-d6) .................................................................... S17
Figure S15. NOESY spectrum of 2 (DMSO-d6) .................................................................. S18
Figure S16. 1H NMR spectrum of 2 (CDCl3, 400MHz) ....................................................... S18
Figure S17. 13
C NMR spectrum of 2 (CDCl3, 100 MHz) .................................................... S19
Figure S18. HMBC spectrum of 2 (CDCl3) ......................................................................... S19
Figure S19. NOESY spectrum of 2 (CDCl3) ........................................................................ S20
Figure S20. IR spectrum of 2 ............................................................................................... S20
Figure S21. HRESIMS spectrum of 2 .................................................................................. S21
Figure S22. 1H NMR spectrum of 3 (DMSO-d6, 400 MHz) ................................................ S21
Figure S23. 13
C NMR spectrum of 3 (DMSO-d6, 100 MHz) ............................................... S22
S3
Figure S24. HMQC spectrum of 3 (DMSO-d6).................................................................... S22
Figure S25. HMBC spectrum of 3 (DMSO-d6) .................................................................... S23
Figure S26. NOESY spectrum of 3 (DMSO-d6) .................................................................. S23
Figure S27. IR spectrum of 3 ............................................................................................... S24
Figure S28. HRESIMS spectrum of 3 .................................................................................. S24
Figure S29. 1H NMR spectrum of 4 (DMSO-d6, 400 MHz) ................................................ S25
Figure S30. 13
C NMR spectrum of 4 (DMSO-d6, 100 MHz) ............................................... S25
Figure S31. HMBC spectrum of 4 (DMSO-d6) .................................................................... S26
Figure S32. NOESY spectrum of 4 (DMSO-d6) .................................................................. S26
Figure S33. 1H NMR spectrum of 4 (CD3OD, 400MHz) ..................................................... S27
Figure S34. 13
C NMR spectrum of 4 (CD3OD, 100 MHz)................................................... S27
Figure S35. HMBC spectrum of 4 (CD3OD) ....................................................................... S28
Figure S36. IR spectrum of 4 ............................................................................................... S28
Figure S37. HRESIMS spectrum of 4 .................................................................................. S29
Figure S38. 1H NMR spectrum of 5 (DMSO-d6, 400 MHz) ................................................ S29
Figure S39. 13
C NMR spectrum of 5 (DMSO-d6, 100 MHz) ............................................... S30
Figure S40. HMBC spectrum of 5 (DMSO-d6) .................................................................... S30
Figure S41. NOESY spectrum of 5 (DMSO-d6) .................................................................. S31
Figure S42. IR spectrum of 5 ............................................................................................... S31
Figure S43. HRESIMS spectrum of 5 .................................................................................. S32
Figure S44. 1H NMR spectrum of 6 (DMSO-d6, 400 MHz) ................................................ S32
Figure S45. 13
C NMR spectrum of 6 (DMSO-d6, 100 MHz) ............................................... S33
Figure S46. HMBC spectrum of 6 (DMSO-d6) .................................................................... S33
Figure S47. IR spectrum of 6 (recorded in acetone) ............................................................ S34
Figure S48. HRESIMS spectrum of 6 .................................................................................. S34
S4
1. Colony and Mycelia of Rhizopycnis vagum Nitaf22
Colony front view Colony back view Mycelia
Note: The fungus grown on PDA medium, and photos taken on day 7.
2. X-ray Crystallographic Data for Rhizopycnolide A (1)
Table S1. Crystal data and structure refinement for rhizopycnolide A (1)
Identification code Rhizopycnolide A
Empirical formula C19H20O9
Formula weight 392.35
Temperature / K 103.1
Crystal system hexagonal
Space group P65
a / Å, b / Å, c / Å 10.9360(4), 10.9360(4), 25.7965(6)
α/°, β/°, γ/° 90, 90, 120
Volume / Å3 2671.83(19)
Z 6
ρcalc / mg mm-3
1.463
μ / mm-1
1.001
F(000) 1236
Crystal size / mm3 0.550 × 0.550 × 0.500
2Θ range for data collection 9.338 to 142.284°
Index ranges -13 ≤ h ≤ 12, -12 ≤ k ≤ 13, -31 ≤ l ≤ 31
Reflections collected 12449
Independent reflections 3430[R(int) = 0.0225 (inf-0.9Å)]
Data/restraints/parameters 3430/1/260
Goodness-of-fit on F2 1.025
Final R indexes [I>2σ (I) i.e. Fo>4σ (Fo)] R1 = 0.0281, wR2 = 0.0731
Final R indexes [all data] R1 = 0.0283, wR2 = 0.0733
Largest diff. peak/hole / e Å-3
0.238/-0.177
Flack Parameters -0.04(6)
Completeness 1.000
20 μm
S5
Table S2. Fractional atomic coordinates (×104) and equivalent isotropic displacement
parameters (Å2×10
3) for rhizopycnolide A (1).
Ueq is defined as 1/3 of the trace of the orthogonalised UIJ tensor.
Atom X Y z U(eq)
O7 3476.8(16) 4633.2(16) 367.0(6) 14.9(3)
O6 5461.5(15) 4664.9(15) 202.7(6) 13.1(3)
O4 10028.4(16) 5491.9(17) -155.9(6) 18.2(3)
O5 6160.8(17) 793.1(16) 201.9(6) 17.7(3)
O1 8147.8(15) 6462.9(15) 179.4(6) 13.0(3)
O8 1952.1(17) -1542.9(16) 1076.5(6) 18.8(3)
O9 1309.0(17) 2384.4(18) 749.3(7) 20.2(4)
O3 8190.2(16) 7334.5(18) -1118.3(6) 19.1(3)
C15 1579(2) 438(2) 935.3(8) 16.7(4)
C11 3577(2) 2583(2) 595.8(8) 13.5(4)
C8 5879(2) 2760(2) 407.2(8) 12.4(4)
C12 4430(2) 1937(2) 608.6(8) 12.8(4)
C14 2424(2) -181(2) 937.7(8) 15.3(4)
C16 2157(2) 1821(2) 761.4(8) 15.0(4)
C10 4117(2) 3986(2) 393.5(8) 12.3(4)
C2 8648(2) 6774(2) -719.3(8) 14.3(4)
O2 9087.8(18) 8663.8(17) -102.9(7) 21.5(4)
C13 3842(2) 565(2) 785.7(8) 14.9(4)
C9 6295(2) 4048(2) 217.1(8) 12.2(4)
C7 6903(2) 2184(2) 417.5(8) 14.1(4)
C3 7607(2) 5216(2) -620.4(8) 13.5(4)
C19 482(3) -2392(2) 1198.2(9) 20.6(5)
C4 7701(2) 5048(2) -28.1(8) 12.9(4)
C17 7378(2) 2157(2) 976.1(9) 17.3(4)
C1 8683(2) 7446(2) -195.9(9) 14.1(4)
C6 8183(2) 3076(2) 66.1(9) 15.6(4)
C5 8797(2) 4654(2) 142.2(9) 14.5(4)
C18 11270(2) 5597(3) 70(1) 25.4(5)
S6
Table S3. Anisotropic displacement parameters (Å2×10
3) for rhizopycnolide A (1).
The anisotropic displacement factor exponent takes the form:
-2π2[h
2a*
2U11+...+2hka×b×U12]
Atom U11 U22 U33 U23 U13 U12
O7 14.8(7) 15.8(7) 17.2(7) -0.6(6) 0.0(6) 10.0(6)
O6 12.1(7) 12.9(7) 16.1(7) 2.4(6) 1.3(6) 7.5(6)
O4 11.2(7) 21.2(8) 22.2(8) 5.2(7) 1.6(6) 8.1(6)
O5 18.8(8) 13.4(7) 23.8(8) -0.7(6) 0.2(6) 10.2(6)
O1 14.1(7) 12.2(7) 13.1(7) 0.0(6) 1.3(6) 6.9(6)
O8 19.1(8) 15.2(7) 18.3(8) 4.0(6) 1.7(6) 5.8(6)
O9 14.0(8) 18.3(8) 28.8(9) 1.8(7) 3.4(6) 8.5(6)
O3 14.2(7) 24.1(8) 19.0(7) 10.4(6) 3.0(6) 9.5(7)
C15 13.1(9) 18.1(11) 14.6(10) 0.5(8) 1.5(8) 4.7(8)
C11 15.3(10) 14.5(10) 10.6(9) -2.1(8) -1.2(8) 7.3(9)
C8 13.1(10) 14.4(10) 10.9(9) -0.5(8) -1.7(8) 7.8(8)
C12 12.9(9) 16.4(10) 9.2(9) -1.0(8) -1.1(8) 7.5(8)
C14 18.7(10) 15.4(10) 8.8(9) 0.3(8) -1.4(8) 6.4(9)
C16 14.3(10) 18.1(11) 12.7(9) -3.2(8) -0.5(8) 8.3(9)
C10 10.5(9) 16.3(10) 10.8(9) -2.7(8) -1.9(7) 7.2(8)
C2 11.0(9) 18.2(10) 14.4(10) 3.1(8) 2.2(8) 7.9(8)
O2 23.6(8) 15.2(8) 23.9(8) 2.7(6) 8.9(7) 8.4(7)
C13 17.3(10) 17.1(10) 11.4(9) 0.5(8) -0.5(8) 9.5(9)
C9 12.4(10) 14.8(10) 11.5(9) -1.8(8) -0.9(8) 8.3(8)
C7 15.4(10) 14.2(10) 15.8(10) 0.6(8) -0.2(8) 9.7(9)
C3 13.1(9) 16.6(10) 12(1) 0.4(8) -0.4(8) 8.4(8)
C19 19.3(11) 17.7(11) 16.8(10) 2.1(9) -2.3(9) 3.2(9)
C4 14.3(10) 11.1(10) 14.1(10) -0.2(8) 0.3(8) 7.0(8)
C17 19.5(10) 19.1(10) 17.2(11) 2.7(8) -1.2(8) 12.6(9)
C1 8.4(9) 15.5(10) 17.8(10) 2.1(8) 2.6(8) 5.5(8)
C6 16.2(10) 18.6(11) 17.4(10) 1.6(8) 0.7(8) 12.7(9)
S7
C5 10.6(9) 17.2(10) 16.7(10) 1.6(8) -0.2(8) 7.6(8)
C18 13.9(11) 38.3(14) 24.9(12) 0.4(11) -1.3(9) 13.7(10)
Table S4. Bond lengths for rhizopycnolide A (1)
Atom Atom Length/Å Atom Atom Length/Å
O7 C10 1.221(3) C11 C10 1.438(3)
O6 C10 1.365(2) C8 C12 1.471(3)
O6 C9 1.379(2) C8 C9 1.338(3)
O4 C5 1.418(3) C8 C7 1.535(3)
O4 C18 1.429(3) C12 C13 1.381(3)
O5 C7 1.431(3) C14 C13 1.399(3)
O1 C4 1.471(2) C2 C3 1.524(3)
O1 C1 1.344(3) C2 C1 1.529(3)
O8 C14 1.358(3) O2 C1 1.199(3)
O8 C19 1.432(3) C9 C4 1.510(3)
O9 C16 1.347(3) C7 C17 1.537(3)
O3 C2 1.412(3) C7 C6 1.539(3)
C15 C14 1.393(3) C3 C4 1.548(3)
C15 C16 1.390(3) C4 C5 1.527(3)
C11 C12 1.425(3) C6 C5 1.519(3)
C11 C16 1.412(3)
Table S5. Bond angles for rhizopycnolide A (1)
Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚
C10 O6 C9 121.32(16) C3 C2 C1 102.41(16)
C5 O4 C18 112.82(17) C12 C13 C14 120.3(2)
C1 O1 C4 111.24(16) O6 C9 C4 108.50(17)
C14 O8 C19 117.19(18) C8 C9 O6 124.36(19)
C16 C15 C14 118.6(2) C8 C9 C4 127.11(19)
C12 C11 C10 121.07(19) O5 C7 C8 106.70(16)
C16 C11 C12 119.95(19) O5 C7 C17 111.15(17)
S8
C16 C11 C10 118.91(19) O5 C7 C6 107.27(17)
C12 C8 C7 121.71(18) C8 C7 C17 110.36(17)
C9 C8 C12 118.01(18) C8 C7 C6 110.44(17)
C9 C8 C7 120.28(19) C17 C7 C6 110.79(18)
C11 C12 C8 117.37(19) C2 C3 C4 103.93(16)
C13 C12 C11 118.76(19) O1 C4 C9 106.97(16)
C13 C12 C8 123.81(19) O1 C4 C3 103.97(16)
O8 C14 C15 123.6(2) O1 C4 C5 107.33(16)
O8 C14 C13 114.62(19) C9 C4 C3 113.27(17)
C15 C14 C13 121.8(2) C9 C4 C5 109.50(17)
O9 C16 C15 117.55(19) C5 C4 C3 115.16(17)
O9 C16 C11 121.89(19) O1 C1 C2 110.78(17)
C15 C16 C11 120.55(19) O2 C1 O1 121.1(2)
O7 C10 O6 115.99(19) O2 C1 C2 128.1(2)
O7 C10 C11 126.16(19) C5 C6 C7 112.88(17)
O6 C10 C11 117.83(18) O4 C5 C4 106.68(17)
O3 C2 C3 112.24(17) O4 C5 C6 113.69(18)
O3 C2 C1 111.31(17) C6 C5 C4 108.67(17)
Table S6. Torsion angles for rhizopycnolide A (1)
A B C D Angle/˚
O6 C9 C4 O1 44.7(2)
O6 C9 C4 C3 -69.2(2)
O6 C9 C4 C5 160.74(17)
O5 C7 C6 C5 161.83(16)
O1 C4 C5 O4 -72.4(2)
O1 C4 C5 C6 164.66(16)
O8 C14 C13 C12 176.49(19)
O3 C2 C3 C4 -145.30(18)
O3 C2 C1 O1 136.96(17)
O3 C2 C1 O2 -41.7(3)
C15 C14 C13 C12 -2.5(3)
C11 C12 C13 C14 1.5(3)
C8 C12 C13 C14 -175.52(19)
C8 C9 C4 O1 -136.9(2)
C8 C9 C4 C3 109.1(2)
C8 C9 C4 C5 -20.9(3)
C8 C7 C6 C5 45.9(2)
C12 C11 C16 O9 -179.10(18)
C12 C11 C16 C15 -0.3(3)
C12 C11 C10 O7 -179.75(19)
S9
C12 C11 C10 O6 1.5(3)
C12 C8 C9 O6 0.8(3)
C12 C8 C9 C4 -177.28(19)
C12 C8 C7 O5 49.5(3)
C12 C8 C7 C17 -71.4(2)
C12 C8 C7 C6 165.77(18)
C14 C15 C16 O9 178.23(19)
C14 C15 C16 C11 -0.6(3)
C16 C15 C14 O8 -176.86(19)
C16 C15 C14 C13 2.0(3)
C16 C11 C12 C8 177.06(18)
C16 C11 C12 C13 -0.1(3)
C16 C11 C10 O7 3.2(3)
C16 C11 C10 O6 -175.56(18)
C10 O6 C9 C8 0.8(3)
C10 O6 C9 C4 179.21(16)
C10 C11 C12 C8 0.0(3)
C10 C11 C12 C13 -177.20(19)
C10 C11 C16 O9 -2.0(3)
C10 C11 C16 C15 176.84(19)
C2 C3 C4 O1 26.6(2)
C2 C3 C4 C9 142.33(18)
C2 C3 C4 C5 -90.5(2)
C9 O6 C10 O7 179.19(18)
C9 O6 C10 C11 -2.0(3)
C9 C8 C12 C11 -1.2(3)
C9 C8 C12 C13 175.9(2)
C9 C8 C7 O5 -131.2(2)
C9 C8 C7 C17 107.9(2)
C9 C8 C7 C6 -15.0(3)
C9 C4 C5 O4 171.84(16)
C9 C4 C5 C6 48.9(2)
C7 C8 C12 C11 178.11(19)
C7 C8 C12 C13 -4.8(3)
C7 C8 C9 O6 -178.47(19)
C7 C8 C9 C4 3.4(3)
C7 C6 C5 O4 176.46(18)
C7 C6 C5 C4 -64.9(2)
C3 C2 C1 O1 16.8(2)
C3 C2 C1 O2 -161.8(2)
S10
C3 C4 C5 O4 42.8(2)
C3 C4 C5 C6 -80.1(2)
C19 O8 C14 C15 3.5(3)
C19 O8 C14 C13 -175.40(18)
C4 O1 C1 C2 0.2(2)
C4 O1 C1 O2 179.03(19)
C17 C7 C6 C5 -76.7(2)
C1 O1 C4 C9 -137.17(17)
C1 O1 C4 C3 -17.1(2)
C1 O1 C4 C5 105.39(18)
C1 C2 C3 C4 -25.83(19)
C18 O4 C5 C4 160.43(18)
C18 O4 C5 C6 -79.8(2)
Table S7. Hydrogen atom coordinates (Å×104) and isotropic displacement parameters
(Å2×10
3) for rhizopycnolide A (1)
Atom X Y z U(eq)
H5 6591 359 275 27
H9 1749 3199 621 30
H3 8892 7936 -1287 29
H15 627 -74 1050 20
H2 9602 6912 -803 17
H13 4402 126 804 18
H3A 7881 4608 -814 16
H3B 6639 4971 -723 16
H19A -83 -2419 899 31
H19B 257 -1985 1496 31
H19C 268 -3353 1282 31
H17A 6548 1595 1194 26
H17B 7905 3123 1111 26
H17C 7986 1735 979 26
H6A 8924 2831 139 19
H6B 7894 2836 -300 19
S11
H5A 9019 4888 518 17
H18A 12099 6261 -131 38
H18B 11196 4666 69 38
H18C 11367 5935 428 38
3. Computation Data for 1-3
1a 1b
ΔG=0.00 kcal/mol, 81.2%
ΔG=0.87 kcal/mol, 18.8%
Figure S1. The stable conformers of rhizopycnolide A (1) with populations greater
than 1% calculated from their relative free energies (ΔG).
2a 2b
ΔG=0.00 kcal/mol, 56.9%
ΔG=0.18 kcal/mol, 42.0%
Figure S2. The stable conformers of rhizopycnolide B (2) with populations greater
than 1% calculated from their relative free energies (ΔG).
S12
(1R, 4R)-3:
(1R, 4R)-3a (1R, 4R)-3b
ΔG=0.00 kcal/mol, 96.6%
ΔG=1.98 kcal/mol, 3.4%
(1R, 4S)-3:
(1R, 4S)-3a (1R, 4S)-3b
ΔG=0.00 kcal/mol, 66.0%
ΔG=0.39 kcal/mol, 34.0%
Figure S3. The stable conformers of (1R, 4R)-3 and (1R, 4S)-3 with populations
greater than 1% calculated from their relative free energies (ΔG).
Figure S4. The experimental ECD spectrum of 3 and the calculated ECD spectra of
(1R, 4S)-3 and (1S, 4R)-3.
S13
4. (1D, 2D) NMR, IR, and HRESIMS Spectra of 1-6
Figure S5. 1H NMR spectrum of 1 (DMSO-d6, 400 MHz)
Figure S6. 13
C NMR spectrum of 1 (DMSO-d6, 100 MHz)
S14
Figure S7. HMQC spectrum of 1 (DMSO-d6)
Figure S8. HMBC spectrum of 1 (DMSO-d6)
S15
Figure S9. NOESY spectrum of 1 (DMSO-d6)
Figure S10. IR spectrum of 1
S16
Figure S11. HRESIMS spectrum of 1
Figure S12. 1H NMR spectrum of 2 (DMSO-d6, 400 MHz)
CH3OH
×
CH3OH
×
S17
Figure S13. 13
C NMR spectrum of 2 (DMSO-d6, 100 MHz)
Figure S14. HMBC spectrum of 2 (DMSO-d6)
CH3OH
×
S18
Figure S15. NOESY spectrum of 2 (DMSO-d6)
Figure S16. 1H NMR spectrum of 2 (CDCl3, 400MHz)
S19
Figure S17. 13
C NMR spectrum of 2 (CDCl3, 100 MHz)
Figure S18. HMBC spectrum of 2 (CDCl3)
S20
Figure S19. NOESY spectrum of 2 (CDCl3)
Figure S20. IR spectrum of 2
S21
m/z Calc m/z Diff(ppm) z Abund Formula Ion
391.1048 391.1035 3.34 -1 258124 C19H19O9 (M-H)-
427.0817 427.0801 3.74 -1 126325.6 C19H20ClO9 (M+Cl)-
429.0799 429.0781 4.08 -1 37636.5 C19H20ClO9 (M+Cl)-
437.1108 437.1089 4.26 -1 61824.3 C20H21O11 (M+HCOO)-
783.2169 783.2142 3.49 -1 30933.7 C38H39O18 (2M-H)-
Figure S21. HRESIMS spectrum of 2
Figure S22. 1H NMR spectrum of 3 (DMSO-d6, 400 MHz)
S22
Figure S23.
13C NMR spectrum of 3 (DMSO-d6, 100 MHz)
Figure S24. HMQC spectrum of 3 (DMSO-d6)
S23
Figure S25. HMBC spectrum of 3 (DMSO-d6)
Figure S26. NOESY spectrum of 3 (DMSO-d6)
S24
Figure S27. IR spectrum of 3
Figure S28. HRESIMS spectrum of 3
S25
Figure S29. 1H NMR spectrum of 4 (DMSO-d6, 400 MHz)
Figure S30. 13
C NMR spectrum of 4 (DMSO-d6, 100 MHz)
S26
Figure S31. HMBC spectrum of 4 (DMSO-d6)
Figure S32. NOESY spectrum of 4 (DMSO-d6)
S27
Figure S33. 1H NMR spectrum of 4 (CD3OD, 400MHz)
Figure S34. 13
C NMR spectrum of 4 (CD3OD, 100 MHz)
S28
Figure S35. HMBC spectrum of 4 (CD3OD)
Figure S36. IR spectrum of 4
S29
m/z Calc m/z Diff(ppm) z Abund Formula Ion
332.0779 332.0776 0.83 -1 250942.4 C16H14NO7 (M-H)-
368.0546 368.0543 1.05 -1 69850.4 C16H15ClNO7 (M+Cl)-
665.1626 665.1624 0.27 -1 8108.4 C32H29N2O14 (2M-H)-
Figure S37. HRESIMS spectrum of 4
Figure S38. 1H NMR spectrum of 5 (DMSO-d6, 400 MHz)
S30
Figure S39. 13
C NMR spectrum of 5 (DMSO-d6, 100 MHz)
Figure S40. HMBC spectrum of 5 (DMSO-d6)
S31
Figure S41. NOESY spectrum of 5 (DMSO-d6)
Figure S42. IR spectrum of 5
S32
Figure S43. HRESIMS spectrum of 5
Figure S44. 1H NMR spectrum of 6 (DMSO-d6, 400 MHz)
S33
Figure S45. 13
C NMR spectrum of 6 (DMSO-d6, 100 MHz)
Figure S46. HMBC spectrum of 6 (DMSO-d6)
S34
Figure S47. IR spectrum of 6 (recorded in acetone)
Figure S48. HRESIMS spectrum of 6