Supporting Information

Supporting Information Bioassay-Guided Isolation of Prenylated Xanthone derivatives from the Leaves of Garcinia oligantha Yue-Xun Tang,,, Wen-Wei Fu,,, Rong Wu,, Hong-Sheng Tan,, Zhen-Wu Shen, and Hong-Xi Xu *,, School of Pharmacy, Shanghai University of Traditional Chinese Medicine, Cai Lun Lu 00, Shanghai 00, People s Republic of China Engineering Research Center of Shanghai Colleges for TCM New Drug Discovery, Cai Lun Lu 00, Shanghai 00, People's Republic of China Correspondence: Prof. Hong-Xi Xu, PhD, School of Pharmacy, Shanghai University of Traditional Chinese Medicine, Cai Lun Lu 00, Shanghai 00, China. E-mail: xuhongxi88@gmail.com Tel: 86 08 Fax: 86 08

List of Supporting Information Part Experimental Section. Computational details Part Results and HRESIMS, ECD, IR, and NMR spectra of compounds Table S. Cytotoxic IC 0 values of crude extracts and key fractions against cancer cell lines Figure CS. ptimized geometries of predominant conformers for (R)- (a h) Table CS. Calculated relative energies (Kcal/mol) and Boltzmann distributions of the optimized compound at BLYP/6-G(d, p) level in gas phase Figure CS. ptimized geometries of predominant conformers for (R, 7R, as, S)- (a g) at the BLYP/6-G(d, p) level in gas phase Table CS. Calculated relative energies (Kcal/mol) and Boltzmann distributions of the optimized compound at BLYP/6-G(d, p) level in gas phase Figure CS. ptimized geometries of predominant conformers for (R, 6R, 8S)-6 (a-h) at the BLYP/6-G(d, p) level in gas phase Table CS. Calculated relative energies (Kcal/mol) and Boltzmann distributions of the optimized compound 6 at BLYP/6-G(d, p) level in gas phase Figure CS. ptimized geometries of predominant conformers for (8S)-7 (a-i) at the BLYP/6- G(d, p) level in gas phase Table CS. Calculated relative energies (Kcal/mol) and Boltzmann distributions of the optimized compound 7 at BLYP/6-G(d, p) level in gas phase Figure S. Structures of gaudichaudione H () and cantleyanone A () Figure S. Key correlations observed in the HMBC and H- H CSY NMR spectra of -

Figure S. Key correlations observed in the HMBC and H- H CSY NMR spectra of compounds 8- Figure S. ECD spectra of compounds, - Figure S6. X-ray crystallographic structure of compound 8 liganthin H () Figure S7. HRESIMS spectrum of Figure S8. Experimental ECD spectrum of Figure S. UV spectrum of spectrum of Figure S. IR (KBr, disc) spectrum of Figure S. H NMR spectrum (pyridine-d, 600 MH Z ) of Figure S. C NMR spectrum (pyridine-d, 0 MH Z ) of Figure S. DEPT NMR spectrum (pyridine-d, 0 MH Z ) of Figure S. HSQC NMR spectrum (pyridine-d, 600 MH Z, 0 MH Z ) of Figure S. HMBC NMR spectrum (pyridine-d, 600 MH Z, 0 MH Z ) of Figure S6. H- H CSY spectrum (pyridine-d, 600 MHz) of Figure S7. NSEY NMR spectrum (pyridine-d, 600 MH Z ) of liganthin I () Figure S8. HRESIMS spectrum of Figure S. UV spectrum of Figure S0. IR (KBr, disc) spectrum of Figure S. H NMR spectrum (pyridine-d, 600 MH Z ) of

Figure S. C NMR spectrum (pyridine-d, 0 MH Z ) of Figure S. DEPT NMR spectrum (pyridine-d, 0 MH Z ) of Figure S. HSQC NMR spectrum (pyridine-d, 600 MH Z, 0 MH Z ) of Figure S. HMBC NMR spectrum (pyridine-d, 600 MH Z, 0 MH Z ) of Figure S6. H- H CSY spectrum (pyridine-d, 600 MH Z ) of liganthin J () Figure S7. HRESIMS spectrum of Figure S8. UV spectrum of Figure S. IR (KBr, disc) spectrum of Figure S0. H NMR spectrum (CDCl, 600 MH Z ) of Figure S. C NMR spectrum (CDCl, 0 MH Z ) of Figure S. DEPT NMR spectrum (CDCl, 0 MH Z ) of Figure S. HSQC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of Figure S. HMBC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of Figure S. H- H CSY spectrum (CDCl, 600 MH Z ) of liganthin K (): Figure S6. HRESIMS spectrum of Figure S7. UV spectrum of Figure S8. IR (KBr, disc) spectrum of Figure S. H NMR spectrum (CDCl, 600 MH Z ) of Figure S0. C NMR spectrum (CDCl, 0 MH Z ) of

Figure S. DEPT NMR spectrum (CDCl, 0 MH Z ) of Figure S. HSQC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of Figure S. HMBC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of Figure S. H- H CSY NMR spectrum (CDCl, 600 MH Z ) of liganthone B (): Figure S. HRESIMS spectrum of Figure S6. Experimental ECD spectrum of Figure S7. UV spectrum of Figure S8. IR (KBr, disc) spectrum of Figure S. H NMR spectrum (CDCl, 600 MH Z ) of Figure S0. C NMR spectrum (CDCl, 0 MH Z ) of Figure S. DEPT NMR spectrum (CDCl, 0 MH Z ) of Figure S. HSQC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of Figure S. HMBC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of Figure S. H- H CSY NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of Figure S. NSEY NMR spectrum (CDCl, 600 MH Z ) of liganthic Acid A (6): Figure S6. HRESIMS spectrum of 6 Figure S7. Experimental ECD spectrum of 6 Figure S8. UV spectrum of 6 Figure S. IR (KBr, disc) spectrum of 6

Figure S60. H NMR spectrum (CDCl, 600 MH Z ) of 6 Figure S6. C NMR spectrum (CDCl, 0 MH Z ) of 6 Figure S6. DEPT NMR spectrum (CDCl, 0 MH Z ) of 6 Figure S6. HSQC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of 6 Figure S6. HMBC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of 6 Figure S6. TCSY NMR spectrum (CDCl, 600 MH Z ) of 6 Figure S66. NSEY NMR spectrum (CDCl, 600 MH Z ) of 6 liganthic Acid B (7): Figure S67. HRESIMS spectrum of 7 Figure S68. Experimental ECD spectrum of 7 Figure S6. UV spectrum of 7 Figure S70. IR (KBr, disc) spectrum of 7 Figure S7. H NMR spectrum (DMS-d 6, 600 MH Z ) of 7 Figure S7. C NMR spectrum (DMS-d 6, 0 MH Z ) of 7 Figure S7. DEPT NMR spectrum (DMS-d 6, 0 MH Z ) of 7 Figure S7. HSQC NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of 7 Figure S7. HMBC NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of 7 Figure S76. TCSY NMR spectrum (DMS-d 6, 600 MH Z ) of 7 Figure S77. NSEY NMR spectrum (DMS-d 6, 600 MH Z ) of 7 liganthic Acid C (8): Figure S78. HRESIMS spectrum of 8 6

Figure S7. Experimental ECD spectrum of 8 Figure S80. UV spectrum of 8 Figure S8. IR (KBr, disc) spectrum of 8 Figure S8. H NMR spectrum (CDCl, 600 MH Z ) of 8 Figure S8. C NMR spectrum (CDCl, 0 MH Z ) of 8 Figure S8. DEPT NMR spectrum (CDCl, 0 MH Z ) of 8 Figure S8. HSQC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of 8 Figure S86. HMBC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of 8 Figure S87. TCSY NMR spectrum (CDCl, 600 MH Z ) of 8 Figure S88. NSEY NMR spectrum (CDCl, 600 MH Z ) of 8 liganthaxthanone A (): Figure S8. HRESIMS spectrum of Figure S0. UV spectrum of Figure S. IR (KBr, disc) spectrum of Figure S. H NMR spectrum (DMS-d 6, 600 MH Z ) of Figure S. C NMR spectrum (DMS-d 6, 0 MH Z ) of Figure S. DEPT NMR spectrum (DMS-d 6, 0 MH Z ) of Figure S. HSQC NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of Figure S6. HMBC NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of Figure S7. H- H CSY NMR spectrum (DMS-d 6, 600 MH Z ) of liganthaxthanone B (): 7

Figure S8. HRESIMS spectrum of Figure S. UV spectrum of Figure S0. IR (KBr, disc) spectrum of Figure S. H NMR spectrum (DMS-d 6, 600 MH Z ) of Figure S. C NMR spectrum (DMS-d 6, 0 MH Z ) of Figure S. DEPT NMR spectrum (DMS-d 6, 0 MH Z ) of Figure S. HSQC NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of Figure S. HMBC NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of Figure S6. H- H CSY NMR spectrum (DMS-d 6, 600 MH Z ) of 8

Supporting Information Available Part Experimental section. Computational details The theoretical calculations for compounds and -7 were performed using Gaussian 0. Conformational analysis was initially carried out using Maestro in Schrödinger 0 conformational searching together with the PLS_00 molecular mechanics methods. The optimized conformation geometries and thermodynamic parameters of all conformations were provided. The top twenty lowest-energy conformers of the PLS_00 conformers were optimized further at the BLYP/6-G (d, p) level. The minimum nature of the structure was confirmed by frequency calculations at the same computational level. The theoretical calculation of ECD was performed using time-dependent density functional theory (TDDFT) at the BLYP/6-G (d, p) level in MeH with PCM model. The calculated ECD curves were generated using SpecDis.6. References: () Gaussian 0, Revision E.0,M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. gliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann,. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. chterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels,. Farkas, J. B. Foresman, J. V. rtiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 0.

() T. Bruhn, A. Schaumlöffel, Y. Hemberger, G. Bringmann, SpecDis version.6, University of Wuerzburg, Germany, 0. Part Results and HRESIMS, IR, NMR, and ECD spectra of compounds Table S. Cytotoxic tests of the key fractions Table S. Cytotoxic IC 0 Values of Crude Extracts and Key Fractions against Cancer Cell Lines a Fraction PC- A.0 B. B >0 Paclitaxel 0.0 a.results are expressed as mean IC 0 values in µg/ml (extracts) or µm (paclitaxel). A: Petroleum ether extracts from the leaves of G. oligantha; B: EtAc-soluble portion of the 0% EtH extract from the leaves of G. oligantha; B: H -soluble portion of the 0% EtH extract from the leaves of G. oligantha. Figure CS ptimized geometries of predominant conformers for (R)- (a h) ptimized geometries of predominant conformers for (a h) at the BLYP/6-G (d, p) level in the gas phase.

Table CS. Calculated relative energies (Kcal/mol) and Boltzmann distributions of the optimized at BLYP/6-G (d, p) level in the gas phase. Calculated Relative Energies (Kcal/mol) and Boltzmann distributions of the optimized at BLYP/6-G (d, p) level in the gas phase. Conformation G ΔE % a -806.87 0. b -806.7 0.077.6 c -806.6 0.07 0. d -806.6 0.08.6 e -806.6 0.7.6 f -806.8 0.87687 6.0 g -806.088.0068.8 h -806.6.8878.6 ΔE: Relative to a; %: Boltzmann distributions, using the relative Gibbs free energies as weighting factors at T = 8. K and atm Figure CS. ptimized geometries of predominant conformers for (R, 7R, as, S)- (a g) at the BLYP/6-G (d, p) level in the gas phase ptimized geometries of predominant conformers for (a g) at the BLYP/6-G (d, p) level in the gas phase

Table CS. Calculated relative energies (Kcal/mol) and Boltzmann distributions of the optimized at BLYP/6-G (d, p) level in the gas phase. Calculated relative energies (Kcal/mol) and Boltzmann distributions of the optimized at BLYP/6-G (d, p) level in the gas phase. Conformation G ΔE % a -60.700 0 7.8 b -60.76 0.7. c -60.68 0.6878. d -60.67 0.708006.6 e -60.6 0.6686 7.70 f -60.68 0.8668 7.67 g -60.76.8078. ΔE: Relative to a; %: Boltzmann distributions, using the relative Gibbs free energies as weighting factors at T = 8. K and atm Figure CS. ptimized geometries of predominant conformers for (R, 6R, 8S)-6 (a h) at the BLYP/6-G (d, p) level in the gas phase ptimized geometries of predominant conformers for 6 (a h) at the BLYP/6-G (d, p) level in the gas phase

Table CS. Calculated relative energies (Kcal/mol) and Boltzmann distributions of the optimized 6 at BLYP/6-G (d, p) level in the gas phase Table CS. Calculated relative energies (Kcal/mol) and Boltzmann distributions of the optimized 6 at BLYP/6-G (d, p) level in the gas phase. Conformation G ΔE % 6a -76. 0. 6b -76.7 0.867877.0 6c -76. 0.886.07 6d -76.6.87 7.6 6e -76..70.8 6f -76...88 6g -76.8.78.76 ΔE: Relative to a; %: Boltzmann distributions, using the relative Gibbs free energies as weighting factors at T = 8. K and atm Figure CS. ptimized geometries of predominant conformers for (8S)-7 (a i) at the BLYP/6-G (d, p) level in the gas phase ptimized geometries of predominant conformers for 7 (a i) at the BLYP/6-G (d, p) level in the gas phase

Table CS. Calculated relative energies (Kcal/mol) and Boltzmann distributions of the optimized 7 at BLYP/6-G (d, p) level in the gas phase Table CS. Calculated relative energies (Kcal/mol) and Boltzmann distributions of the optimized 7 at BLYP/6-G (d, p) level in the gas phase. Conformation G ΔE % 7a -768.87 0 6.7 7b -768.6 0.807 8.6 7c -768. 0.7706.6 7d -768. 0.767. 7e -768.87 0.60.70 7f -768.6 0.880 6.0 7g -768.8.088. 7h -768.068.87.7 7i -768.00.7688. ΔE: Relative to a; %: Boltzmann distributions, using the relative Gibbs free energies as weighting factors at T = 8. K and atm Figure S. Structures of gaudichaudione H () and cantleyanone A (). H H Me H Me H gaudichaudione H cantleyanone A Figure S. Key correlations observed in the HMBC and H- H CSY NMR spectra of - H H H H H H H H H H C HMBC H-H CSY

Figure S. Key correlations observed in the HMBC and H- H CSY NMR spectra of 8-. H CH H H H H H H H C HMBC H-H CSY 8 Figure S. ECD spectra of compounds, - ECD spectra of compounds oliganthone B (), gaudichaudione H () and cantleyanone ()

Figure S6. X-ray crystallographic structure of compound 8 Crystal structure of (±) oliganthic acid C. (a) Crystal packing of 8 showing the nonsuperimposition of (8S)-8 and (8R)-8. (b) RTEP diagram of 8S-oliganthic acid C ((8S)-8) 6

Figure S7. HRESIMS spectrum of Figure S8. Experimental ECD spectrum of 7

Figure S. UV spectrum of spectrum of Figure S. IR (KBr, disc) spectrum of 8

Figure S. H NMR spectrum (pyridine-d, 600 MH Z ) of.0.7.00...6.8....0.0.0.8.0.08.0..0 8.7 Pyridine-d 7.08 7.06 6.6.8.6.....8.7......0.0.8.8.88.86..8.7.6.....0.8.88.8.8.80.7.7.67.6...0.0.8 H H H...... 8. 7. 6...... 0. -0. Figure S. C NMR spectrum (pyridine-d, 0 MH Z ) of 80.6 6. 60.0 7.7.8 0.6 0. Pyridine-d.8 8.0.6.7 7.8. 0..7.8.7 6..00 0. 78.. 0. 8. 8. 8.60 8.7 7.0 6.7 6. 8.6 8.0 6. 00 0 80 70 60 0 0 0 0 0 0 80 70 60 0 0 0 0 0

Figure S. DEPT NMR spectrum (pyridine-d, 0 MH Z ) of Figure S. HSQC NMR spectrum (pyridine- d, 600 MH Z, 0 MH Z ) of 0 0 0 60 80 0 0 {8.7,0.}Pyridine-d 0 60 80 00 0 6 8 7 6 f (ppm) 0 - - - 0

Figure S. HMBC NMR spectrum (pyridine-d, 600 MH Z, 0 MH Z ) of 0 0 0 60 80 0 0 {8.7,0.}Pyridine-d 0 60 80 00 0 8 7 f (ppm) 6 Figure S6. H- H CSY spectrum (pyridine-d, 600MHz) of {8.7,8.7}Pyridine-d 6 7 8 8 7 f (ppm) 6

Figure S7. NESY spectrum (pyridine-d, 600MHz) of Figure S8. HRESIMS spectrum of Figure S. UV spectrum of 0. Absorbance (AU) 0. 0. 0. 80 0. 0.0 0 0 60 80 00 0 0 60 Wavelength (nm)

Figure S0. IR (KBr, disc) spectrum of Figure S. H NMR spectrum (pyridine-d, 600 MH Z ) of 0.6..00...6.0 6.0 6.06 6.0.0 8.7 Pyridine-d 7.0 7.0 6.6.6...8.6.0.88.87.86.6....6..8 H H H..0..0..0..0..0..0 8. 8.0 7. 7.0 6. 6.0..0..0..0..0..0 0.

Figure S. C NMR spectrum (pyridine-d, 0 MH Z ) of 80.6 6.0 60.0 7.7.86 0. Pyridine-d 7...0 7.8 0.08..68 6..00 0. 78.. 8.7 8.6 6.8 8.6 0 00 0 80 70 60 0 0 0 0 0 0 80 70 60 0 0 0 0 0 - Figure S. DEPT NMR spectrum (pyridine-d, 0 MH Z ) of

Figure S. HSQC NMR spectrum (pyridine-d, 600 MH Z, 0 MH Z ) of 0 0 0 60 80 0 0 {8.7,0.}Pyridine-d 0 60 80 00 0 6 8 7 6 f (ppm) 0 - - - Figure S. HMBC NMR spectrum (pyridine-d, 600 MH Z, 0 MH Z ) of 0 0 0 60 80 0 0 {8.7,0.}Pyridine-d 0 60 80 00 0 8 7 f (ppm) 6

Figure S6. H- H CSY NMR spectrum (pyridine-d, 600 MH Z ) of {8.7,8.7}Pyridine-d 6 7 8 8 7 f (ppm) 6 Figure S7. HRESIMS spectrum of 6

Figure S8. UV spectrum of Figure S. IR (KBr, disc) spectrum of 7

Figure S0. H NMR spectrum (CDCl, 600 MH Z ) of Figure S C NMR spectrum (CDCl, 0 MH Z ) of 00. 7. 6. 6.87.66 6.8.06.0.7.0.8. 8.07 7..6.0.66 77.6 CDCl. 7.80..76.6 8. 8.0 00 0 80 70 60 0 0 0 0 0 0 80 70 60 0 0 0 0 0 8

Figure S. DEPT NMR spectrum (CDCl, 0 MH Z ) of Figure S. HSQC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of 0 0 0 {7.6,77.6}CDCl 60 80 0 0 0 60 80 00 8 7 6 f (ppm) 0

Figure S. HMBC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of 0 0 0 {7.6,77.6}CDCl 60 80 0 0 0 60 80 00 0 8 7 6 f (ppm) 0 - Figure S. H- H CSY spectrum (CDCl, 600 MH Z ) of 6 {7.6,7.6}CDCl 7 8.0..0 8. 8.0 7. 7.0 6. 6.0..0 f (ppm)..0..0..0..0 0

Figure S6. HRESIMS spectrum of Figure S7. UV spectrum of 0.8 0.7 Absorbance (AU) 0.6 0. 0. 0. 0. 0. 0 0 60 80 00 0 0 60 0 8 Wavelength (nm) Figure S8. IR (KBr, disc) spectrum of

Figure S. H NMR spectrum (CDCl, 600 MH Z ) of 0. 0.8.00 0.86.07.0.0..08.07.08.. 7.6 CDCl 6. 6. 6...0.8.66.6.6..0.6....8.8.7.77.87.78..8 H H H..0..0..0..0..0 8. 8.0 7. 7.0 6. 6.0..0..0..0..0..0 0. 0.0 Figure S0. C NMR spectrum (CDCl, 0 MH Z ) of 0.8 7.80 60. 60.8.7..87.6. 7.8 6.60 8.8..6.8 77.6 CDCl 6.0 8.0.6.8.0 8. 8.0 00 0 80 70 60 0 0 0 0 0 0 80 70 60 0 0 0 0 0

Figure S. DEPT NMR spectrum (CDCl, 0 MH Z ) of Figure S. HSQC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of 0 0 0 0 60 {7.6,77.6}CDCl 70 80 0 0 0 0 0 0 60 70 80 0 8 7 6 f (ppm)

Figure S. HMBC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of {7.6,77.6}CDCl 0 0 0 0 60 70 80 0 0 0 0 0 0 60 70 80 0 00 8 7 6 f (ppm) 0 Figure S. H- H CSY NMR spectrum (CDCl, 600 MH Z ) of {7.6,7.6}CDCl 6 7 8 8 7 6 f (ppm)

Figure S. HRESIMS spectrum of Figure S6. Experimental ECD spectrum of

Figure S7. UV spectrum of Figure S8. IR (KBr, disc) spectrum of 6

Figure S. H NMR spectrum (CDCl, 600 MH Z ) of 0..0..00...00...0.7.08.07.07.06.08.0. 7.0 7.0 7.6 CDCl 6.6 6.6 6.0.7..8.6..6..8.7.7.6..7..6...8..0 H..0..0..0..0..0 8. 8.0 7. 7.0 6. 6.0..0..0..0..0..0 0. 0.0-0. Figure S0. C NMR spectrum (CDCl, 0 MH Z ) of 0.67 78.7 6. 6.0.0.6.6.0 7.7 7.6.8.8. 8. 8.6 8. 8. 8.7 78.7 77.6 CDCl..8 0.6 0.0.8.6 8.7 8..7 6.7 00 0 80 70 60 0 0 0 0 0 0 80 70 60 0 0 0 0 0 7

Figure S. DEPT NMR spectrum (CDCl, 0 MH Z ) of Figure S. HSQC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of {7.6,77.6}CDCl 0 0 0 0 60 70 80 0 0 0 0 0 0 60 70 80 0 00 8 7 6 f (ppm) 8

Figure S. HMBC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of {7.6,77.6}CDCl 0 0 0 0 60 70 80 0 0 0 0 0 0 60 70 80 0 00 8 7 6 f (ppm) Figure S. H- H CSY spectrum (CDCl, 600 MH Z ) of

Figure S. NESY NMR spectrum (CDCl, 600 MH Z ) of {7.6,7.6}CDCl 6 7 8 8 7 6 f (ppm) Figure S6. HRESIMS spectrum of 6 0

Figure S7. Experimental ECD spectrum of 6 Figure S8. UV spectrum of 6

Figure S. IR (KBr, disc) spectrum of 6 Figure S60. H NMR spectrum (CDCl, 600 MH Z ) of 6 0.6.00.0.0 0..07.0.0.0.07.0.08.8.0..6.0.0..8.0.0. 7.6 CDCl 6.....0....8.8.8.......8.6.......8.80.7.78.70.70.68.66.66...0....8.8.7.6.. H H H H..0..0..0..0 8. 8.0 7. 7.0 6. 6.0..0..0..0..0..0 0. 0.0

Figure S6. C NMR spectrum (CDCl, 0 MH Z ) of 6 8. 7. 66. 6..8..0 0...7.0.6 7.8 6.0.67.7.7 0. 77.6 CDCl 6...8 0.07.7.8 6.7.88.7.80.87 8.07 7.78 6.6 0 80 70 60 0 0 0 0 0 0 80 70 60 0 0 0 0 0 Figure S6. DEPT NMR spectrum (CDCl, 0 MH Z ) of 6

Figure S6. HSQC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of 6 0 0 0 {7.6,77.6}CDCl 60 80 0 0 0 60 80 00 0 8 7 6 f (ppm) 0 Figure S6. HMBC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of 6 {0.00,-0.00} 0 0 0 60 80 0 0 0 60 80 00 0 8 7 6 f (ppm) 0 -

Figure S6. TCSY NMR spectrum (CDCl, 600 MH Z ) of 6 {7.6,7.6}CDCl 6 7 8 8 7 6 f (ppm) Figure S66. NESY NMR spectrum (CDCl, 600 MH Z ) of 6 0 {7.6,7.6}CDCl 6 7 8 8 7 6 0 f (ppm)

Figure S67. HRESIMS spectrum of 7 Figure S68. Experimental ECD spectrum of 7 6

Figure S6. UV spectrum of 7 Figure S70. IR (KBr, disc) spectrum of 7 7

Figure S7. H NMR spectrum (DMS-d 6, 600 MH Z ) of 7.00.08..7...0..0.08 6....00.08. 6....0.0.0.00.87...6.6..7.0 DMS-d6...77.... H H H.0..0..0..0..0 8. 8.0 7. 7.0 6. 6.0..0..0..0..0..0 0. 0.0 Figure S7. C NMR spectrum (DMS-d 6, 0 MH Z ) of 7 8

Figure S7. DEPT NMR spectrum (DMS-d 6, 0 MH Z ) of 7 Figure S7. HSQC NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of 7 0 {.0,.}DMS-d6 0 0 0 60 70 80 0 0 0 0 0 0 60 70 80 0 8 7 6 f (ppm)

Figure S7. HMBC NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of 7 0 {.0,.}Dimethyl Sulfoxide-d6 0 0 0 60 70 80 0 0 0 0 0 0 60 70 80 0.0..0..0..0 8. 8.0 7. 7.0 6. 6.0..0..0..0..0..0 f (ppm) Figure S76. TCSY NMR spectrum (DMS-d 6, 600 MH Z ) of 7 {.0,.0}DMS-d6 6 7 8 8 7 f (ppm) 6 0

Figure S77. NESY NMR spectrum (DMS-d 6, 600 MH Z ) of 7 {.0,.0}DMS-d6 6 7 8 8 7 6 f (ppm) Figure S78. HRESIMS spectrum of 8

Figure S7. Experimental ECD spectrum of 8 Figure S80. UV spectrum of 8 0. Absorbance (AU) 0. 0. 86 0. 0. 0 0 60 80 00 0 0 60 Wavelength (nm)

Figure S8. IR (KBr, disc) spectrum of 8 Figure S8. H NMR spectrum (CDCl, 600 MH Z ) of 8.0.00.07.08..6.0.06.0 6.8.8 7.6 CDCl 6.8 6.8 6..7..0..0..7.7.7..8... H H 8 7 6 0

Figure S8. C NMR spectrum (CDCl, 0 MH Z ) of 8 8.7 8. 7. 6. 60.7.... 7.70 7..67 0.. 6.6.68 0. 78.67 77.6 CDCl 8. 6..0 8. 8. 6.0..7 7.8 00 0 80 70 60 0 0 0 0 0 0 80 70 60 0 0 0 0 0 Figure S8. DEPT NMR spectrum (CDCl, 0 MH Z ) of 8

Figure S8. HSQC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of 8 B-q 0 0 0 {7.6,77.}cdcl 60 80 0 0 0 60 80 00 8.0 7. 7.0 6. 6.0..0..0..0..0..0 0. 0.0 f (ppm) Figure S86. HMBC NMR spectrum (CDCl, 600 MH Z, 0 MH Z ) of 8 {-0.00,0.00} 0 0 0 60 80 0 0 0 60 80 8.0 7. 7.0 6. 6.0..0..0. f (ppm).0..0..0 0. 0.0-0.

Figure S87. TCSY NMR spectrum (CDCl, 600 MH Z ) of 8 Figure S88. NESY NMR spectrum (CDCl, 600 MH Z ) of 8 6

Figure S8. HRESIMS spectrum of Figure S0. UV spectrum of 8 0. 0. Absorbance (AU) 0. 0. 6 0. 0 0 60 80 00 0 0 60 Wavelength (nm) Figure S. IR (KBr, disc) spectrum of 7

Figure S. H NMR spectrum (DMS-d 6, 600 MH Z ) of.0.00.0..6.8.8.. 6.0..8 7. 7. 7.0 6.8.7.7....8.88....0 DMS-d6.7.67... H H.0..0..0..0..0..0 8. 8.0 7. 7.0 6. 6.0..0..0..0..0..0 0. 0.0-0. Figure S. C NMR spectrum (DMS-d 6, 0 MH Z ) of 8.78 6..7 0.7 6.8.6.6..7.0 6.8.8..76.. 0. 8.0 78.. DMS-d6. 7.88 7.07..07 7. 00 0 80 70 60 0 0 0 0 0 0 80 70 60 0 0 0 0 0 8

Figure S. DEPT NMR spectrum (DMS-d 6, 0 MH Z ) of Figure S. HSQC NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of 0 {.0,.}DMS-d6 0 0 60 80 0 0 0 60 80 00 0.0 8. 8.0 7. 7.0 6. 6.0..0..0..0..0..0 0. 0.0-0. -.0 f (ppm)

Figure S6. HMBC NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of 0 {.0,.}Dimethyl Sulfoxide-d6 0 0 0 60 70 80 0 0 0 0 0 0 60 70 80 0 7.0 6. 6.0..0..0 f (ppm)..0..0..0 Figure S7. H- H CSY NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of 0 {.0,.0}DMS-d6 6 7 7. 7.0 6. 6.0..0..0. f (ppm).0..0..0 0. 0.0 60

Figure S8. HRESIMS spectrum of Figure S. UV spectrum of 6

Figure S0. IR (KBr, disc) spectrum of Figure S. H NMR spectrum (DMS-d 6, 600 MH Z ) of 0.80 0. 0..06.00...86 6.. H H H.0 Dimethyl Sulfoxide-d6.7.60 H.86 7.6 7..7.7.6.6. 6..0..0..0..0..0..0 8. 8.0 7. 7.0 6. 6.0..0..0..0..0..0 0. 0.0 6

Figure S. C NMR spectrum (DMS-d 6, 0 MH Z ) of 8. 6. 8. 0.... 0.6. 6.7. 8.7..7. 0.7 7.8 77.8. Dimethyl Sulfoxide-d6 7.7.6.7 8.0 0 80 70 60 0 0 0 0 0 0 80 70 60 0 0 0 0 Figure S. DEPT NMR spectrum (DMS-d 6, 0 MH Z ) of 6

Figure S. HSQC NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of 0 {.0,.}DMS-d6 0 0 0 60 70 80 0 0 0 0 0 0 60 70 80 0 8 7 f (ppm) 6 Figure S. HMBC NMR spectrum (DMS-d 6, 600 MH Z, 0 MH Z ) of {.0,.}DMS-d6 0 0 0 0 60 70 80 0 0 0 0 0 0 60 70 80 8 7 f (ppm) 6 6

Figure S6. H- H CSY NMR spectrum (DMS-d 6, 600 MH Z ) of {.0,.0}DMS-d6 6 7 8 8 7 f (ppm) 6 6