Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2015 Electronic Supplementary Information Natural Thioredoxin Reductase Inhibitors from Jatropha integerrima Jian-Yong Zhu, a Lan-Lan Lou, a Yan-Qiong Guo, a Wei Li, a Yan-Hong Guo, b Jing-Mei Bao, a Gui-Hua Tang, a Xian-Zhang Bu, a and Sheng Yin a a School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou, Guangdong 510006, P.R.China E-mail: yinsh2@mail.sysu.edu.cn; Fax: 86-20-39943090; Tel: 86-20-39943090. b School of Chinese Materia Medica, Guangzhou University of Chinese Medicine, Guangzhou, Guangdong 510405, P. R. China E-mail: yinsh2@mail.sysu.edu.cn; Fax: 86-20-39943090; Tel: 86-20-39943090. These authors have contributed equally to this work. 1
Contents: S1. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone A (1) S2. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone A (1) S3. 1 H- 1 H COSY spectrum of jatrointelone A (1) in CDCl 3 S4. HSQC spectrum of jatrointelone A (1) in CDCl 3 S5. HMBC spectrum of jatrointelone A (1) in CDCl 3 S6. NOESY spectrum of jatrointelone A (1) in CDCl 3 S7. HRESIMS spectrum of jatrointelone A (1) S8. IR (KBr disc) spectrum of jatrointelone A (1) S9. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone B (2) S10. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone B (2) S11. 1 H- 1 H COSY spectrum of jatrointelone B (2) in CDCl 3 S12. HSQC spectrum of jatrointelone B (2) in CDCl 3 S13. HMBC spectrum of jatrointelone B (2) in CDCl 3 S14. NOESY spectrum of jatrointelone B (2) in CDCl 3 S15. HRESIMS spectrum of jatrointelone B (2) S16. IR (KBr disc) spectrum of jatrointelone B (2) S17. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone C (3) S18. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone C (3) S19. 1 H- 1 H COSY spectrum of jatrointelone C (3) in CDCl 3 S20. HSQC spectrum of jatrointelone C (3) in CDCl 3 S21. HMBC spectrum of jatrointelone C (3) in CDCl 3 S22. NOESY spectrum of jatrointelone C (3) in CDCl 3 S23. HRESIMS spectrum of jatrointelone C (3) S24. IR (KBr disc) spectrum of jatrointelone C (3) S25. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone D (4) S26. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone D (4) S27. 1 H- 1 H COSY spectrum of jatrointelone D (4) in CDCl 3 S28. HSQC spectrum of jatrointelone D (4) in CDCl 3 2
S29. HMBC spectrum of jatrointelone D (4) in CDCl 3 S30.NOESY spectrum of jatrointelone D (4) in CDCl 3 S31. HRESIMS spectrum of jatrointelone D (4) S32. IR (KBr disc) spectrum of jatrointelone D (4) S33. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone E (5) S34. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone E (5) S35. 1 H- 1 H COSY spectrum of jatrointelone E (5) in CDCl 3 S36. HSQC spectrum of jatrointelone E (5) in CDCl 3 S37. HMBC spectrum of jatrointelone E (5) in CDCl 3 S38. NOESY spectrum of jatrointelone E (5) in CDCl 3 S39. HRESIMS spectrum of jatrointelone E (5) S40. IR (KBr disc) spectrum of jatrointelone E (5) S41. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone F (6) S42. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone F (6) S43. 1 H- 1 H COSY spectrum of jatrointelone F (6) in CDCl 3 S44. HSQC spectrum of jatrointelone F (6) in CDCl 3 S45. HMBC spectrum of jatrointelone F (6) in CDCl 3 S46. NOESY spectrum of jatrointelone F (6) in CDCl 3 S47. HRESIMS spectrum of jatrointelone F (6) S48. IR (KBr disc) spectrum of jatrointelone F (6) S49. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone G (7) S50. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone G (7) S51. 1 H- 1 H COSY spectrum of jatrointelone G (7) in CDCl 3 S52. HSQC spectrum of jatrointelone G (7) in CDCl 3 S53. HMBC spectrum of jatrointelone G (7) in CDCl 3 S54. NOESY spectrum of jatrointelone G (7) in CDCl 3 S55. HRESIMS spectrum of jatrointelone G (7) S56. IR (KBr disc) spectrum of jatrointelone G (7) S57. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone H (8) S58. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone H (8) 3
S59. 1 H- 1 H COSY spectrum of jatrointelone H (8) in CDCl 3 S60. HSQC spectrum of jatrointelone H (8) in CDCl 3 S61. HMBC spectrum of jatrointelone H (8) in CDCl 3 S62. NOESY spectrum of jatrointelone H (8) in CDCl 3 S63. HRESIMS spectrum of jatrointelone H (8) S64. IR (KBr disc) spectrum of jatrointelone H (8) S65. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone I (9) S66. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone I (9) S67. 1 H- 1 H COSY spectrum of jatrointelone I (9) in CDCl 3 S68. HSQC spectrum of jatrointelone I (9) in CDCl 3 S69. HMBC spectrum of jatrointelone I (9) in CDCl 3 S70. NOESY spectrum of jatrointelone I (9) in CDCl 3 S71. HRESIMS spectrum of jatrointelone I (9) S72. IR (KBr disc) spectrum of jatrointelone I (9) S73. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 10 S74. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 10 S75. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 11 S76. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 11 S77. 1 H NMR (400 MHz, CD 3 OD) spectrum of 12 S78. 13 C NMR (100 MHz, CD 3 OD) spectrum of 12 S79. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 13 S80. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 14 S81. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 14 S82. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 15 S83. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 15 S84. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 16 S85. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 16 S86. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 17 S87. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 17 S88. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 18 4
S89. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 18 S90. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 19 S91. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 19 S92. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 20 S93. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 20 S94. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 21 S95. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 21 S96. CD and UV spectra of compound 2 in MeOH. S97. (A) The Rh 2 (OCOCF 3 ) 4 induced CD spectrum of 3 in CH 2 Cl 2 S98. The CD spectra of 3, 4, and 5 in MeOH S99. The CD spectra of 3a, 6, and 7 in MeOH S100. 1 H NMR (400 MHz, CD 3 COCD 3 ) spectrum of 8a S101. ESIMS spectrum of 8a S102. 1 H NMR (400 MHz, CD 3 OD) spectrum of 9a S103. ESIMS spectrum of 9a S104. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 3a S105. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 3a S106. HSQC spectrum of 3a in CDCl 3 S107. HMBC spectrum of 3a in CDCl 3 S108. NOESY spectrum of 3a in CDCl 3 S109. ESIMS spectrum of 3a S110. HRESIMS spectrum of 3a S111. IR (KBr disc) spectrum of 3a S112 The TrxR inhibitory curves of the most active compounds 17 and 19 5
S1. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone A (1) O HO O H HO 6
10.1 11.7 16.4 20.9 28.6 28.8 29.0 29.1 33.4 35.8 37.8 47.9 S2. 13 C NMR (100 MHz, CDCl3) spectrum of jatrointelone A (1) 7 213.2 199.3 132.5 140.3 149.5 160.2 81.8 71.6
S3. 1 H- 1 H COSY spectrum of jatrointelone A (1) in CDCl 3 f1 (ppm) 8
S4. HMQC spectrum of jatrointelone A (1) in CDCl 3 f1 (ppm) 9
S5. HMBC spectrum of jatrointelone A (1) in CDCl 3 10
S6. NOESY spectrum of jatrointelone A (1) in CDCl 3 f1 (ppm) 11
S7. HRESIMS spectrum of jatrointelone A (1) YJIZ-97D #432 RT: 3.59 AV: 1 NL: 2.67E7 F: FTMS + p ESI Full ms [50.00-1500.00] 355.1889 26000000 24000000 22000000 20000000 18000000 315.1963 16000000 Intensity 14000000 12000000 10000000 8000000 687.3879 6000000 4000000 2000000 0 385.1994 269.1906 239.1435 423.1764 653.3465 717.3990 883.7700 1068.5619 1295.0089 1464.2124 200 400 600 800 1000 1200 1400 m/z 12
S8. IR (KBr disc) spectrum of jatrointelone A (1) 105 100 95 507.49cm-1 3173.18cm-1 528.13cm-1 90 2933.77cm-1 1230.78cm-1 % T 85 1436.65cm-1 1375.24cm-1 971.23cm-1 793.84cm-1 694.34cm-1 80 1656.72cm-1 1273.49cm-1 1061.90cm-1 869.96cm-1 747.94cm-1 914.89cm-1 75 1681.90cm-1 70 4000 3500 3000 2500 2000 1500 1000 500 名称 Administrator 157 说明样品 157 用户 Administrator 日期星期二, 十月 28 2014 cm-1 1634.45cm-1 1090.17cm-1 13
S9. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone B (2) O HO O HO 14
S10. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone B (2) YJIZ-94-20140905 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 0 15
S11. 1 H- 1 H COSY spectrum of jatrointelone B (2) in CDCl 3 YJIZ-94-20140907 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 f2 (ppm) 3.5 3.0 2.5 2.0 1.5 1.0 0.5 16
S12. HSQC spectrum of jatrointelone B (2) in CDCl 3 f1 (ppm) 17
S13. HMBC spectrum of jatrointelone B (2) in CDCl 3 f1 (ppm) 18
S14. NOESY spectrum of jatrointelone B (2) in CDCl 3 YJIZ-94-20140907 0 1 2 3 4 5 6 7 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 f2 (ppm) 3.5 3.0 2.5 2.0 1.5 1.0 0.5 19
S15. HRESIMS spectrum of jatrointelone B (2) YJIZ-94 #387 RT: 3.22 AV: 1 NL: 1.35E6 F: FTMS + p ESI Full ms [50.00-1500.00] Intensity 2100000 2000000 1900000 1800000 1700000 1600000 1500000 1400000 1300000 1200000 1100000 1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0 329.1751 331.1908 346.2096 347.1858 348.1891 353.1728 354.1761 361.2012 357.2043 317.2113 332.1942 343.1908 351.1571 365.1131 321.1694 335.2219 327.1959 341.1736 320 325 330 335 340 345 350 355 360 365 m/z 20
S16. IR (KBr disc) spectrum of jatrointelone B (2) 120 110 100 1010.27cm-1 1041.97cm-1 % T 90 80 70 2972.68cm-1 1076.31cm-1 1503.31cm-1 866.83cm-1 1342.10cm-1 905.96cm-1 1621.33cm-1 1381.08cm-1 1111.82cm-1 1297.46cm-1 1271.71cm-1 1215.83cm-1 1711.11cm-1 667.07cm-1 540.32cm-1 60 50 40 750.95cm-1 30 4000 3500 3000 2500 2000 1500 1000 500 名称 YJIZ-94 说明样品 150 用户 Administrator 日期星期二, 十月 28 2014 cm-1 21
1.57 1.14 3.13 1.18 2.85 3.18 3.38 2.39 S17. 1 H NMR (400 MHz, CDCl3) spectrum of jatrointelone C (3) 22 1.00 0.99 1.00 5.59 5.60 5.62 5.62 4.43 4.43 4.44 4.45 3.78 3.79 3.10 3.12 1.95 1.95 2.28 2.30 2.31 1 04 1.12 1.14 1.14 1.34 1.49 1.52 HO O O
S18. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone C (3) 23
S19. 1 H- 1 H COSY spectrum of jatrointelone C (3) in CDCl 3 f1 (ppm) 24
S20. HSQC spectrum of jatrointelone C (3) in CDCl 3 YJIZ-81-20140901 10 20 30 40 50 60 70 80 90 100 110 120 130 140 5.8 5.4 5.0 4.6 4.2 3.8 3.4 f2 (ppm) 3.0 2.6 2.2 1.8 1.4 1.0 25
S21. HMBC spectrum of jatrointelone C (3) in CDCl 3 YJIZ-81-20140901 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 6.0 5.5 5.0 4.5 4.0 3.5 3.0 f2 (ppm) 26 2.5 2.0 1.5 1.0 0.5
S22. NOESY spectrum of jatrointelone C (3) in CDCl 3 f1 (ppm) 27
S23. HRESIMS spectrum of jatrointelone C (3) YJIZ-81 #461 RT: 3.68 AV: 1 NL: 2.03E7 T: FTMS + p ESI Full ms [250.00-850.00] 120 110 100 337.1766 90 339.1921 Relative Abundance 80 70 60 50 40 30 20 10 0 349.2365 317.2103 340.1956 331.2260 350.2397 335.2208 353.1713 313.2153 318.2135 332.2291 347.2208 311.1629 321.1815 325.1766 329.2103 341.1988 357.2025 360.2523 310 315 320 325 330 335 340 345 350 355 360 m/z 28
S24. IR (KBr disc) spectrum of jatrointelone C (3) 110 105 100 95 539.31cm-1 % T 90 2962.23cm-1 1455.82cm-1 1110.11cm-1 860.18cm-1 666.96cm-1 85 80 1712.42cm-1 1613.62cm-1 1380.67cm-1 1300.56cm-1 1201.24cm-1 1257.39cm-1 75 753.04cm-1 70 4000 3500 3000 2500 2000 1500 1000 500 名称 YJIZ-81 说明样品 147 用户 Administrator 日期星期二, 十月 28 2014 cm-1 29
S25. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone D (4) O OH HO O 30
87.7 58.6 63.6 65.4 16.2 18.3 27.9 29.0 36.2 38.7 39.6 S26. 13 C NMR (100 MHz, CDCl3) spectrum of jatrointelone D (4) 31 194.4 140.8 141.9 142.8 149.1
S27. 1 H- 1 H COSY spectrum of jatrointelone D (4) in CDCl 3 f1 (ppm) 32
S28. HSQC spectrum of jatrointelone D (4) in CDCl 3 20 30 40 50 60 70 80 90 100 110 120 130 140 150 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 f2 (ppm) 3.5 3.0 2.5 2.0 1.5 1.0 0.5 33
S29. HMBC spectrum of jatrointelone D (4) in CDCl 3 f1 (ppm) 34
S30.NOESY spectrum of jatrointelone D (4) in CDCl 3 YJIZ-6-20140329 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 f2 (ppm) 35 3.0 2.5 2.0 1.5 1.0 0.5
S31. HRESIMS spectrum of jatrointelone D (4) YJIZ-6 #189 RT: 1.50 AV: 1 NL: 2.68E7 T: FTMS + p ESI Full ms [200.00-1000.00] 26000000 355.1877 24000000 22000000 20000000 18000000 Intensity 16000000 14000000 12000000 10000000 315.1951 8000000 6000000 333.2058 371.1616 357.2024 365.2319 4000000 2000000 0 297.1845 313.1796 301.2159 317.2102 329.2108 347.2213 335.2211 373.1598 379.2476 387.2138 389.1725 403.1878 290 300 310 320 330 340 350 360 370 380 390 400 410 m/z 36
S32. IR (KBr disc) spectrum of jatrointelone D (4) 3480.19 1642.39 1529.72 1090.32 759.31 Single channel 0.2 0.4 0.6 0.8 1.0 3500 3000 2500 2000 1500 1000 Wavenumber cm-1 D:\ 朱建勇 \YJIZ-6.1 YJIZ-6 solid 23/06/2014 Page 1/1 37
S33. 1 H NMR (400 MHz, CDCl3) spectrum of jatrointelone E (5) 1.00 1.01 1.12 2.07 1.21 0.92 5.58 5.60 4.44 4.45 3.79 3.09 3.11 3.20 3.45 1.10 2.99 0.75 3.12 2.31 2.35 2.37 1.98 2.82 2.23 3.00 5.59 1.14 1.16 1.35 O OH HO O 38
S34. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone E (5) YJIZ-28-20140405 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 39
S35. 1 H- 1 H COSY spectrum of jatrointelone E (5) in CDCl 3 f1 (ppm) 40
S36. HSQC spectrum of jatrointelone E (5) in CDCl 3 f1 (ppm) 41
S37. HMBC spectrum of jatrointelone E (5) in CDCl 3 f1 (ppm) 42
S38. NOESY spectrum of jatrointelone E (5) in CDCl 3 f1 (ppm) 43
S39. HRESIMS spectrum of jatrointelone E (5) yjiz-28a #98 RT: 0.79 AV: 1 NL: 9.63E7 T: FTMS + c ESI Full ms [200.00-800.00] Relative Abundance 100 95 90 85 80 75 70 65 60 55 50 45 40 35 687.38544 30 671.39075 25 20 355.18741 15 567.30463 633.33856 745.46356 10 705.39600 373.19772 621.35187 555.31732 301.14023 5 413.26529 289.15311 339.19232 473.34378 517.36987 763.47437 0 200 250 300 350 400 450 500 550 600 650 700 750 800 m/z 44
S40. IR (KBr disc) spectrum of jatrointelone E (5) 3480.77 3404.92 1725.52 1638.55 1366.76 1219.56 789.75 Transmittance [%] 20 40 60 80 100 3500 3000 2500 2000 1500 1000 Wavenumber cm-1 D:\ 朱建勇 \YJIZ-28.1 YJIZ-28 solid 23/06/2014 Page 1/1 45
S41. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone F (6) YJIZ-64-20140617 O HO O O 6.2 6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 f1 (ppm) 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0. 46
75.5 12.7 16.4 17.4 19.2 26.1 26.8 29.1 29.1 36.9 36.9 42.3 60.6 63.1 S42. 13 C NMR (100 MHz, CDCl3) spectrum of jatrointelone F (6) 47 208.8 192.5 162.2 136.2 137.8 145.8
S43. 1 H- 1 H COSY spectrum of jatrointelone F (6) in CDCl 3 YJIZ-64-20140619 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 f2 (ppm) 3.5 3.0 2.5 2.0 1.5 1.0 0.5 48
S44. HSQC spectrum of jatrointelone F (6) in CDCl 3 YJIZ-64-20140619 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 7.0 6.5 6.0 5.5 5.0 4.5 4.0 f2 (ppm) 3.5 3.0 2.5 2.0 1.5 1.0 49
S45. HMBC spectrum of jatrointelone F (6) in CDCl 3 f1 (ppm) 50
S46. NOESY spectrum of jatrointelone F (6) in CDCl 3 YJIZ-64-20140619 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 6.5 6.0 5.5 5.0 4.5 4.0 f2 (ppm) 3.5 3.0 2.5 2.0 1.5 1.0 51
S47. HRESIMS spectrum of jatrointelone F (6) 52
S48. IR (KBr disc) spectrum of jatrointelone F (6) 2964.97 2178.04 1709.89 1602.46 1442.25 1375.03 1189.40 741.78 Transmittance [%] 90 92 94 96 98 100 102 3500 3000 2500 2000 1500 1000 Wavenumber cm-1 D:\ 朱建勇 \YJIZ-64-20140623.1 YJIZ-64-20140623 23/06/2014 Page 1/1 53
S49. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone G (7) YJIZ-97A-20141016 O HO O O 7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 f1 (ppm) 3.8 3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 54
75.2 61.6 63.8 12 5 16.5 17.1 19.3 25.0 29.2 29.9 37.0 37.3 42.5 S50. 13 C NMR (100 MHz, CDCl3) spectrum of jatrointelone G (7) 55 208.4 192.1 164.8 135.2 137.7 148.4
S51. 1 H- 1 H COSY spectrum of jatrointelone G (7) in CDCl 3 YJIZ-97A-20141020 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 f2 (ppm) 3.5 3.0 2.5 2.0 1.5 1.0 56
S52. HSQC spectrum of jatrointelone G (7) in CDCl 3 YJIZ-97A-20141021 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 6.5 6.0 5.5 5.0 4.5 4.0 3.5 f2 (ppm) 3.0 2.5 2.0 1.5 1.0 0.5 57
S53. HMBC spectrum of jatrointelone G (7) in CDCl 3 f1 (ppm) 58
S54. NOESY spectrum of jatrointelone G (7) in CDCl 3 YJIZ-97A-20141018 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 6.5 6.0 5.5 5.0 4.5 4.0 3.5 f2 (ppm) 3.0 2.5 2.0 1.5 1.0 59
S55. HRESIMS spectrum of jatrointelone G (7) YJIZ-97A #401 RT: 3.34 AV: 1 NL: 8.94E6 F: FTMS + p ESI Full ms [50.00-1500.00] 353.1729 8500000 8000000 7500000 7000000 6500000 6000000 5500000 Intensity 5000000 4500000 4000000 683.3560 3500000 3000000 2500000 313.1804 2000000 1500000 1000000 500000 0 631.3246 279.1596 421.1603 101.0959 531.3876 717.3167 846.7808 1045.8058 1151.1963 1356.4803 200 400 600 800 1000 1200 1400 m/z 60
S56. IR (KBr disc) spectrum of jatrointelone G (7) 105 104 102 100 98 % T 96 1609.33cm-1 1719.83cm-1 509.98cm-1 542.95cm-1 667.99cm-1 94 1034.60cm-1 770.45cm-1 92 90 4000 3500 3000 2500 2000 1500 1000 500 名称 Administrator 155 说明样品 155 用户 Administrator 日期星期二, 十月 28 2014 cm-1 61
2.90 3.02 3.01 2.02 3.00 1.08 3.88 S57. 1 H NMR (400 MHz, CDCl3) spectrum of jatrointelone H (8) 62 1.06 1.00 0.96 1.01 1.04 5.19 5.20 4.67 4.67 4.68 3.94 3.97 4.09 4.12 3.24 3.26 3.28 2.11 2.31 2.48 2.49 2.52 2.53 0.91 0.95 0.96 1.13 1.27 1.28 OH H O O O H
S58. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone H (8) YJIZ-91B-20140901 210 200 190 180 170 160 150 140 130 120 110 f1 (ppm) 100 90 80 70 60 50 40 30 20 10 63
S59. 1 H- 1 H COSY spectrum of jatrointelone H (8) in CDCl 3 YJIZ-91B-20141006 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 5.5 5.0 4.5 4.0 3.5 3.0 f2 (ppm) 2.5 2.0 1.5 1.0 0.5 64
S60. HSQC spectrum of jatrointelone H (8) in CDCl 3 YJIZ-91B-20141006 10 20 30 40 50 60 70 80 90 100 110 120 6.5 6.0 5.5 5.0 4.5 4.0 3.5 f2 (ppm) 3.0 2.5 2.0 1.5 1.0 65
S61. HMBC spectrum of jatrointelone H (8) in CDCl 3 f1 (ppm) 66
S62. NOESY spectrum of jatrointelone H (8) in CDCl 3 f1 (ppm) 67
S63. HRESIMS spectrum of jatrointelone H (8) YJIZ-91A #466 RT: 3.72 AV: 1 NL: 2.94E7 T: FTMS + p ESI Full ms [250.00-850.00] 377.1712 100 Relative Abundance 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 355.1893 588.4078 701.4915 731.3533 814.5753 15 10 393.1451 475.3239 295.1681 5 401.1947 551.2537 679.5096 267.1711 327.1942 455.2024 491.2980 604.3818 0 763.3431 792.5933 830.5491 250 300 350 400 450 500 550 600 650 700 750 800 850 m/z 68
S64. IR (KBr disc) spectrum of jatrointelone H (8) % T 110 108 106 104 102 100 98 96 94 92 90 88 86 84 82 80 4000 3500 3000 2500 2000 1500 1000 500 名称 Administrator 158 2961.75cm-1 说明样品 158 用户 Administrator 日期星期二, 十月 28 2014 cm-1 1656.87cm-1 1634.79cm-1 1683.14cm-1 1376.03cm-1 1462.05cm-1 1262.26cm-1 668.06cm-1 970.69cm-1 802.62cm-1 748.48cm-1 869.86cm-1 1090.65cm-1 914.88cm-1 573.69cm-1 69
S65. 1 H NMR (400 MHz, CDCl 3 ) spectrum of jatrointelone I (9) OH O H H O O 70
S66. 13 C NMR (100 MHz, CDCl 3 ) spectrum of jatrointelone I (9) YJIZ-91A-20140901 210 200 190 180 170 160 150 140 130 120 110 f1 (ppm) 100 90 80 70 60 50 40 30 20 10 71
S67. 1 H- 1 H COSY spectrum of jatrointelone I (9) in CDCl 3 YJIZ-91A-20140923 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.0 5.5 5.0 4.5 4.0 3.5 3.0 f2 (ppm) 2.5 2.0 1.5 1.0 0.5 0.0 72
S68. HSQC spectrum of jatrointelone I (9) in CDCl 3 YJIZ-91A-20140923 10 20 30 40 50 60 70 80 90 100 110 120 5.4 5.0 4.6 4.2 3.8 3.4 3.0 f2 (ppm) 2.6 2.2 1.8 1.4 1.0 0.6 73
S69. HMBC spectrum of jatrointelone I (9) in CDCl 3 f1 (ppm) 74
S70. NOESY spectrum of jatrointelone I (9) in CDCl 3 YJIZ-91A-20140923 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 5.5 5.0 4.5 4.0 3.5 f2 (ppm) 3.0 2.5 2.0 1.5 1.0 0.5 75
S71. HRESIMS spectrum of jatrointelone I (9) yjiz-91a #418 RT: 3.47 AV: 1 NL: 1.71E6 T: FTMS + p ESI Full ms [50.00-1000.00] 170 160 150 140 130 120 Relative Abundance 110 100 90 80 70 355.1907 60 50 40 30 20 10 0 239.2251 351.1573 367.1894 295.1693 335.1623 385.2010 225.6683 245.6684 274.2742 318.3006 412.6646 220 240 260 280 300 320 340 360 380 400 420 440 m/z 76
S72. IR (KBr disc) spectrum of jatrointelone I (9) % T 110 108 106 104 102 100 98 96 94 92 90 88 86 84 82 80 4000 3500 3000 2500 2000 1500 1000 500 名称 Administrator 158 2961.75cm-1 说明样品 158 用户 Administrator 日期星期二, 十月 28 2014 cm-1 1656.87cm-1 1634.79cm-1 1683.14cm-1 1376.03cm-1 1462.05cm-1 1262.26cm-1 668.06cm-1 970.69cm-1 802.62cm-1 748.48cm-1 869.86cm-1 1090.65cm-1 914.88cm-1 573.69cm-1 77
S73. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 10 OH H O H 78
13.3 15.8 16.1 17.1 19.5 21.4 26.0 27.7 28.2 28.4 30.2 30.4 33.5 33.6 42.4 42.6 S74. 13 C NMR (100 MHz, CDCl3) spectrum of 10 79 208.5 131.0 132.5 136.8 137.4 145.6 146.0 150.2 114.8
4.13 2.93 1.63 1.29 2.64 3.31 2.76 S75. 1 H NMR (400 MHz, CDCl3) spectrum of 11 80 1.17 1.00 5.11 5.12 5.16 5.23 4.60 4.61 4.61 1.00 3.11 3.13 3.15 3.17 2.20 2.20 2.55 2.56 2.57 2.58 1.51 1.53 1.72 1.73 1.76 0 74 0.75 0.84 0.85 1.17 1.21 OH O
S76. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 11 210 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 0-10 81
S77. 1 H NMR (400 MHz, CD 3 OD) spectrum of 12 OH O CH 2 OH 82
72.5 12 3 13.8 16.3 17.3 22.2 23.9 26.2 26.5 31.7 34.7 43.6 S78. 13 C NMR (100 MHz, CD3OD) spectrum of 12 83 211.2 132.3 134.2 134.9 137.2 139.9 147.1 147.5 152.7 115.6
S79. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 13 OH O CHO 84
S80. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 14 O H H HO O 85
S81. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 14 YJIZ-99-20140910 210 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 0 86
0.94 1.31 3.72 3.27 2.54 S82. 1 H NMR (400 MHz, CDCl3) spectrum of 15 87 1.00 1.04 2.12 7.26 5.83 5.84 5.85 5.85 4.71 4.79 4.80 4.80 1.02 4.17 1.16 1.18 1.55 1.80 1.81 1.81 O H H O
14.6 18.7 19.4 34.5 36.2 36.5 39.6 43.6 45.8 51.7 S83. 13 C NMR (100 MHz, CDCl3) spectrum of 15 88 211.9 198.2 136.2 136.5 140.8 146.8 148.6 148.8 158.4 108.1 113.2
S84. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 16 O H H O 6.2 6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 f1 (ppm) 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 89
S85. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 16 90
S86. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 17 HO O H H O 91
74.5 18.7 19.4 26.1 34.5 36.6 43.3 43.6 45.3 51.9 S87. 13 C NMR (100 MHz, CDCl3) spectrum of 17 92 212.1 197.9 136.7 141.0 145.3 146.6 148.5 158.0 108.1 113.4
S88. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 18 HO O H H O 93
72.9 18.7 19.5 23.9 34.2 36.2 42.9 43.7 45.5 51.4 S89. 13 C NMR (100 MHz, CDCl3) spectrum of 18 94 209.1 197.3 137.4 140.7 145.8 146.7 148.1 158.2 109.0 113.3
S90. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 19 YJIZ-47-20140515 O H H HO O A (t) 4.87 6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 f1 (ppm) 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0. 95
S91. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 19 YJIZ-47-20140515 210 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 0-10 96
1.04 2.02 3.87 3.25 3.60 3.16 S92. 1 H NMR (400 MHz, CDCl3) spectrum of 20 97 1.00 1.04 1.03 2.00 1.01 4.74 4.82 4.84 4.84 5.32 5.32 5.33 5.33 5.87 5.88 5.88 5.89 4.11 3.19 3.22 2.59 2.61 2.61 2.62 1.59 1.84 1.84 1.84 1.18 1.20 O H HO O H
S93. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 20 98
0.99 1.05 3.57 3.67 1.59 3.26 2.52 1.32 1.13 1.15 S94. 1 H NMR (400 MHz, CDCl3) spectrum of 21 99 1.00 1.09 0.94 0.91 0.88 1.21 6.72 6.72 5.58 4.45 4.76 4.81 4.82 4.86 4.87 3.26 3.27 1.48 1.48 1.49 1.66 2.01 2.01 2.34 2.34 2.46 2.72 2.75 O H H O OH
79.4 33.2 35.7 39.5 41.3 50.8 55.5 16.8 19.0 19.4 S95. 13 C NMR (100 MHz, CDCl3) spectrum of 21 100 201.2 194.3 147.0 147.0 153.2 131.3 132.1 133.7 106.0 112.3
S96. CD and UV spectra of compound 2 in MeOH. Stereoview of 2: arrows denote the electric transition dipole of the chromophores. 101
S97. (A) The Rh 2 (OCOCF 3 ) 4 induced CD spectrum of 3 in CH 2 Cl 2. (B) The CD spectrum of 3 in MeOH 102
S98. The CD spectra of 3, 4, and 5 in MeOH 103
S99. The CD spectra of 3a, 6, and 7 in MeOH 104
4.07 1.94 2.81 2.88 3.36 S100. 1 H NMR (400 MHz, CD3COCD3) spectrum of 8a 105 0.96 1.00 2.65 5.06 4.56 3.31 3.48 3.55 3.58 1.76 1.79 2.31 2.52 2.57 2.58 2.59 2.60 2.61 2.62 0.88 0.89 1.17 1.18 1.29
S101. EIMS spectrum of 8a 106
S102. 1 H NMR (400 MHz, CD3COCD3) spectrum of 9a YJIZ-91AF-20150318 5.6 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 2.8 f1 (ppm) 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 107
S103. EIMS spectrum of 9a 108
S104. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 3a in CDCl 3 YJIZ-81F O O O 6.4 6.2 6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 f1 (ppm) 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0. 109
S105. 13 C NMR (100 MHz, CDCl 3 ) spectrum of 3a in CDCl 3 YJIZ-81F 210 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 0-10 110
S106. HSQC spectrum of 3a in CDCl 3 YJIZ-81-20140901 10 20 30 40 50 60 70 80 90 100 110 120 130 140 5.8 5.4 5.0 4.6 4.2 3.8 3.4 f2 (ppm) 3.0 2.6 2.2 1.8 1.4 1.0 111
S107. HMBC spectrum of 3a in CDCl 3 YJIZ-81F 20 40 60 80 100 120 140 160 180 200 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 f2 (ppm) 3.5 3.0 2.5 2.0 1.5 1.0 112
S108. NOESY spectrum of 3a in CDCl 3 f1 (ppm) 113
S109. ESIMS spectrum of 3a 114
S110. HRESIMS spectrum of 3a yjiz-81f2 #222 RT: 2.10 AV: 1 NL: 3.19E3 T: FTMS - p ESI Full ms [200.00-800.00] Intensity 18000 17000 16000 15000 14000 13000 12000 11000 10000 9000 8000 7000 6000 5000 4000 3000 313.1790 2000 1000 0 310.5 311.0 311.5 312.0 312.5 313.0 313.5 314.0 314.5 315.0 315.5 m/z 115
S111. IR (KBr disc) spectrum of 3a % T 111 105 100 95 90 85 80 75 70 65 60 55 50 3471.26cm-1 3557.01cm-1 2940.78cm-1 2974.92cm-1 46 4000 3500 3000 2500 2000 1500 1000 500 cm-1 116 1714.01cm-1 1452.57cm-1 1366.16cm-11161.04cm-1 1262.72cm-1 1244.86cm-1 940.55cm-1 854.27cm-1 669.34cm-1 708.81cm-1 567.99cm-1
S112 The TrxR inhibitory curves of the most active compounds 17 and 19. 117