Chukvelutins A-C, 16-norphragmalin limonoids with unprecedented skeletons from Chukrasia tabularis var. velutina

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1 Chukvelutins A-C, 16-norphragmalin limonoids with unprecedented skeletons from Chukrasia tabularis var. velutina Jun Luo, Jun-Song Wang, Jian-Guang Luo, Xiao-Bing Wang, and Ling-Yi Kong* Department of Natural Medicinal Chemistry, China Pharmaceutical University, 24 Tong Jia Xiang, Nanjing , People s Republic of China * Corresponding author: Tel.: ; fax: address: cpu_lykong@126.com 1

2 Supporting Information S3. Experimental section S4. IR (KBr disc) spectrum of Chukvelutin A (1) S5. 1 H NMR spectrum of Chukvelutin A (1) in CDCl 3 S6. 13 C NMR spectrum of Chukvelutin A (1) in CDCl 3 S7. HSQC spectrum of Chukvelutin A (1) in CDCl 3 S8. HMBC spectrum of Chukvelutin A (1) in CDCl 3 S9. NOESY spectrum of Chukvelutin A (1) in CDCl 3 S10. ESIMS spectrum of Chukvelutin A (1) S11. HRESIMS spectrum of Chukvelutin A (1) S12. IR (KBr disc) spectrum of Chukvelutin B (2) S13. 1 H NMR spectrum of Chukvelutin B (2) in CDCl 3 S C NMR spectrum of Chukvelutin B (2) in CDCl 3 S15. HSQC spectrum of Chukvelutin B (2) in CDCl 3 S16. HMBC spectrum of Chukvelutin B (2) in CDCl 3 S17. NOESY spectrum of Chukvelutin B (2) in CDCl 3 S18. ESIMS spectrum of Chukvelutin B (2) S19. HRESIMS spectrum of Chukvelutin B (2) S20. IR (KBr disc) spectrum of Chukvelutin C (3) S21. 1 H NMR spectrum of Chukvelutin C (3) in CDCl 3 S C NMR spectrum of Chukvelutin C (3) in CDCl 3 S23. HSQC spectrum of Chukvelutin C (3) in CDCl 3 S24. HMBC spectrum of Chukvelutin C (3) in CDCl 3 S25. NOESY spectrum of Chukvelutin C (3) in CDCl 3 S26. ESIMS spectrum of Chukvelutin C (3) S27. HRESIMS spectrum of Chukvelutin C (3) 2

3 S3. Experimental section 3.1. General experimental procedures IR (KBr-disks) spectra were recorded by Bruker Tensor 27 spectrometer. UV spectra were recorded quantitatively on a Shimadzu UV-2501 PC spectrophotometer. Optical rotations were measured with a JASCO P-1020 polarimeter. NMR spectra were recorded on Bruker ACF-500 NMR instrument ( 1 H: 500 MHz, 13 C: 125 MHz) with TMS as internal standard. Mass spectra were obtained on a MS Agilent 1100 Series LC/MSD Trap mass spectrometer (ESI-MS) and a Mariner ESI-TOF spectrometer (HRESIMS), respectively. All solvents used were of analytical grad (Jiangsu Hanbang Sci. & Tech. Co. Ltd). Silica gel (Qingdao Haiyang Chemical Co. Ltd), Sephadex LH-20 (Pharmacia), and RP-C 18 (40 63 μm, FuJi) were used for column chromatography. Preparative HPLC was carried out using Agilent 1100 Series with Shim-park RP-C 18 column ( mm) and 1100 Series Multiple Wavelength detector Plant material The air-dried stem barks of Chukrasia tabularis var. velutina were collected from Xishuangbanna, Yunnan Province, China, and were authenticated by Professor Mian Zhang of Research Department of Pharmacognosy, China Pharmaceutical University. A voucher specimen (NO MML) has been deposited in the Department of Natural Medicinal Chemistry, China Pharmaceutical University Extraction and isolation The air-dried stem barks (10 kg) were extracted with refluxing 95% ethanol, and the crude extract (2000g) was partitioned between CHCL 3 and H 2 O to obtain the chloroform extract (300 g). After removal of the fatty components by extracting with petroleum ether (PE), 210 g of extraction was obtained. It was fractionated via a silica gel column eluted with CHCl 3 /MeOH in gradient (1:0 to 1:2) to afford eight fractions according to TLC monitor. Fr. C (22 g) was chromatographed on a column of silica gel eluted successively with a gradient of PE/EtOAc (4:1 to 1:2) to give eight sub-fractions (Fr. C1 C8). Fr. C7 was chromatographed on a column of reversed-phase C 18 silica gel eluted with MeOH/H 2 O (5:5 to 7:3) to give three sub-fractions (Fr. C7a C7e), then Fr. C7c was separated by preparative HPLC using CH 3 CN /H 2 O (55:45, 10 ml/min) as the mobile phase to give 1 (8 mg), 3 (6 mg), and a mixture contained 2, then the mixture was pured by CH 3 OH/H 2 O (65:35, 10 ml/min) as the mobile phase to give 2 (8 mg). 3

4 S4. IR (KBr disc) spectrum of Chukvelutin A (1) 4

5 S5. 1 H NMR spectrum of Chukvelutin A (1) in CDCl 3 5

6 S6. 13 C NMR spectrum of Chukvelutin A (1) in CDCl 3 6

7 S7. HSQC spectrum of Chukvelutin A (1) in CDCl 3 7

8 S8. HMBC spectrum of Chukvelutin A (1) in CDCl 3 8

9 S9. NOESY spectrum of Chukvelutin A (1) in CDCl 3 9

10 S10. ESIMS spectrum of Chukvelutin A (1) 10

11 S11. HRESIMS spectrum of Chukvelutin A (1) 11

12 S12. IR (KBr disc) spectrum of Chukvelutin B (2) 12

13 S13. 1 H NMR spectrum of Chukvelutin B (2) in CDCl 3 13

14 S C NMR spectrum of Chukvelutin B (2) in CDCl 3 14

15 S15. HSQC spectrum of Chukvelutin B (2) in CDCl 3 15

16 S16. HMBC spectrum of Chukvelutin B (2) in CDCl 3 16

17 S17. NOESY spectrum of Chukvelutin B (2) in CDCl 3 17

18 S18. ESIMS spectrum of Chukvelutin B (2) 18

19 S19. HRESIMS spectrum of Chukvelutin B (2) 19

20 S20. IR (KBr disc) spectrum of Chukvelutin C (3) 20

21 S21. 1 H NMR spectrum of Chukvelutin C (3) in CDCl 3 21

22 S C NMR spectrum of Chukvelutin C (3) in CDCl 3 22

23 S23. HSQC spectrum of Chukvelutin C (3) in CDCl 3 23

24 S24. HMBC spectrum of Chukvelutin C (3) in CDCl 3 24

25 S25. NOESY spectrum of Chukvelutin C (3) in CDCl 3 25

26 S26. ESIMS spectrum of Chukvelutin C (3) 26

27 S27. HRESIMS spectrum of Chukvelutin C (3) 27