Enantiomeric Lignans and Neolignans from Phyllanthus glaucus: Enantioseparation and Their Absolute Configurations Zhaodi Wu, 1,* Yongji Lai, 2,* Lei Zhou, 1 Ye Wu, 1 Hucheng Zhu, 1 Zhengxi Hu, 1 Jing Yang, 3 Jinwen Zhang, 4 Jianping Wang, 1 Zengwei Luo, 1 Yongbo Xue, 1 and Yonghui Zhang 1 1 Hubei Key Laboratory of Natural Medicinal Chemistry and Resource Evaluation, School of Pharmacy, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 433, Hubei Province, People s Republic of China. 2 Department of Pharmacy, the Central Hospital of Wuhan, Wuhan 4314, Hubei Province, People s Republic of China. 3 State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 6524, People s Republic of China. 4 Tongji Hospital Affiliated to Tongji Medical College,Huazhong University of Science and Technology,Wuhan 433, People s Republic of China. * These authors contributed equally to the work. Correspondence and requests for materials should be addressed to Y. Z. (zhangyh@mails.tjmu.edu.cn) or Y. X. (yongboxue@mail.hust.edu.cn)
CONTENTS ECD Calculations for compound 7R,8R-2 at LC-wPBE/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level... 3 ECD Calculations for compound 7R,8R-2 at CAM-B3LYP/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level... 12 ECD Calculations for compound 7R,8R-2 at WB97XD/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level... 14 HRESIMS, UV, IR, and NMRspectra of 1... 17 HRESIMS, UV, IR, and NMRspectra of 2... 21 HRESIMS, UV, IR, and NMRspectra of 3... 26 HRESIMS, UV, IR, and NMRspectra of 4... 3 HRESIMS, UV, IR, and NMRspectra of 5... 35 HRESIMS, UV, IR, and NMRspectra of 6... 4 HRESIMS, UV, IR, and NMRspectra of 7... 45 HRESIMS, UV, IR, and NMRspectra of 8... 51 Chiral HPLC separation profiles of 1a/1b 8a/8b... 56
ECD Calculation a b c d e f g h i Figure S1. Optimized geometries of predominant conformers for compound 7R,8R-2 at the B3LYP/6-311++G(2d,p) level in MeOH using the IEFPCM solvation model. 3
Table S1. Important thermodynamic parameters (a.u.) and Boltzmann distributions of the optimized compound 7R,8R-2 calculated at LC-wPBE/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level in MeOH with IEFPCM solvation model. Conformations E+ZPE G % a -1149.74778-115.513587 1.6 b -1149.745583-115.512212.33 c -1149.746992-115.513539 1.46 d -1149.745532-115.512444.31 e -1149.749154-115.516256 14.42 f -1149.747124-115.513755 1.68 g -1149.75597-115.517638 66.49 h -1149.745795-115.512478.41 i -1149.74977-115.516285 13.29 E is the total electronic energy in MeOH at LC-wPBE/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level with IEFPCM solvation model, ZPE is the zero point energy in MeOH at B3LYP/6-311++G(2d,p) level with IEFPCM solvation model, and G is the Gibbs free energy by the sum of E and the thermal correction obtained at B3LYP/6-311++G(2d,p) level. %: Boltzmann distributions, using the relative Gibbs free energies as weighting factors. Table S2. Optimized coordinates of 7R,8R-2 in MeOH (Å) at B3LYP/6-311++G(2d,p) level using IEFPCM solvation model. a b C 1.695498 1.24566 1.78171 C 1.67583 1.35759 1.746384 C 2.8427 1.541562 1.6386 C 2.799466 1.576151.98533 C 3.191554.662256.17627 C 3.23664.666481.5268 C 2.4616.496755.245978 C 2.47375.49682.214971 C 1.32864.79433.523855 C 1.32455.763933.54362 C.95966.8742 1.537985 C.93971.14348 1.52225 O 3.524426 2.678883 1.246672 O 3.518926 2.717797 1.26834 C.53834 2.58741.242261 C.534214 2.36236.277196 C 2.91844 1.447399.28392 C 2.885122 1.45242.36374 C 1.748658.9644.327432 C 1.74852.969.33532 C.651544 1.922162.75313 C.639859 1.915356.7461 C 3.92884.591632.6895 C 3.919885.6441.7271 C 3.818266.7733.46269 C 3.832285.7543.453785 C 2.669767 1.279674.165758 C 2.69868 1.26727.194735 C 1.648883.421643.552194 C 1.67985.416639.578957 4
O 1.1884 1.762871 3.15269 O 1.172235 1.86662 3.81661 C.147378 1.652868 2.177396 C.13245 1.66414 2.149827 O 4.82649 1.611198.842955 O 4.848235 1.589682.833245 O.273 2.634262 1.431116 O.24363 2.581589 1.47112 C.976848 3.246757 2.2643 C.937241 3.17661 2.332145 O 4.38728 1.55428.73297 O 4.336188 1.36132.679125 C 4.78716.227515 1.767643 C 4.82899.17445 1.76484 O 2.6838 2.638176.333267 O 2.72961 2.623488.3878 C 1.579351 3.252129 1.5812 C 1.64744 3.237786 1.8865 H 1.413473 1.927916 2.574125 H 1.38463 2.1125 2.514184 H 2.774711 1.186513 1.19148 H 2.799177 1.28825.961765 H.9884.13618 2.153888 H.6636.59185 2.127321 H 4.25983 2.76777.616429 H 4.266546 2.72544.5965 H 1.227237 2.78566.21731 H 1.227221 2.77587.1471 H 3.5869 2.511568.457369 H 2.972127 2.514467.51148 H 1.95843 2.921461.771855 H 1.75356 2.91891.758298 H 4.821886.976854 1.156849 H 4.82113.9941 1.19415 H.765368.829455 1.21838 H.83412.827273 1.74522 H 1.876158 1.122731 2.928632 H.841772 1.672538 3.966455 H.337469.67477 2.253365 H.3684.65257 2.251537 H.59632 2.47539 2.453459 H.78723 2.36994 2.358388 H 4.571194 2.51388.6522 H 4.68613 2.489812.5677 H 1.7125 2.521781 2.6383 H 1.665777 2.444726 2.694552 H 1.5386 4.44585 1.727355 H 1.471499 3.98786 1.822196 H.44464 3.67655 3.111933 H.39591 3.5865 3.18737 H 5.656689.7378 2.16965 H 5.715498.66183 2.13954 H 4.23345.128323 2.548467 H 4.892.53329 2.5874 H 5.62468.76723 1.397231 H 5.98697.82695 1.299525 H 1.482868 2.867876 2.23887 H 1.55928 2.834334 2.9955 H.64844 3.9289.458974 H.75656 3.99553.551863 H 1.84842 4.31582 1.35915 H 1.88684 4.29728 1.13669 c d C 1.48245 1.44433 1.779465 C 1.814898 1.961531 1.156591 C 2.61233 1.751249 1.4989 C 3.91679 1.88552.625962 C 3.77911.845913.74167 C 3.537934.67157.7664 C 2.42482.34953.135928 C 2.695271.432899.54333 C 1.249196.656349.598228 C 1.395356.3543.569379 C.82477.24871 1.556298 C.97124.853668 1.125458 O 3.277639 2.925974 1.262788 O 3.916255 2.97855.657971 C.528827 1.968754.33779 C.489591 1.569161.525943 C 2.932596 1.545927.161481 C 1.234458.722924 1.38693 C 1.772852 1.13139.396848 C 1.51597.46556.6983 C.65433 1.924753.729364 C.533718 1.621861.645454 5
C 4.27578.738356.465717 C 2.16453 1.761543 1.42683 C 3.979584.619743.25784 C 3.3836 1.632797.785289 C 2.823523 1.17442.364673 C 3.68513.44731.94246 C 1.734712.364897.658944 C 2.75361.584245.59296 O.86483 2.69228 2.47939 O.74318 3.1634 2.9867 C.61565 1.653573 2.13332 C.148423 1.85875 2.398 O 5.54766 1.414324.498479 O 4.295413 2.652471.8395 O.5914 2.58191 1.521471 O.27685 1.72426 1.725441 C.8867 3.62899 2.426572 C.53677 2.12118 2.848489 O 4.2925 1.254118.5833 O 4.821276.79685.42898 C 4.764463.395386 1.577546 C 5.374277.47975.968892 O 2.89816 2.525393.578511 O 4.917485.434569.493245 C 1.792733 3.18332 1.236 C 5.312512.728522 1.22248 H 1.139774 2.147519 2.529448 H 1.48857 2.897976 1.592726 H 2.769557 1.58335.86633 H 3.55443 1.373256.34285 H.75781.1641 2.143743 H.21884.928795 1.547143 H 4.39185 2.956589.66475 H 4.761379 2.7224.255924 H 1.26655 2.685179.41281 H 1.126662 2.45784.41513 H 2.988643 2.6831.36525 H.28597.85956 1.883427 H.994641 2.946965.744718 H 1.11673 2.526217.447795 H 4.92642 1.159319.9263 H 1.94611 2.679169 1.959194 H.848223.88687 1.87286 H 2.983273 1.499347.468355 H 1.24353 2.512774 3.363344 H 1.666755 3.113186 1.83982 H.898517 1.644195 2.838515 H.611986 1.81596 2.783921 H.435991.68561 2.185433 H.892331 1.89847 2.224654 H 4.83451 2.32143.239216 H 5.77226 2.37658.329742 H 1.581435 2.35443 2.8224 H 1.255887 1.37714 3.111264 H 1.4684 3.866351 1.949856 H 1.716 3.76269 2.656564 H.321527 3.473799 3.262957 H.18674 2.241546 3.682478 H 5.6455.91268 1.96169 H 6.38399.22926 1.277361 H 4.51641.228982 2.38832 H 4.79635.82989 1.837674 H 5.62798.562326 1.145116 H 5.41137 1.282382.228816 H 1.68489 2.76885 2.19811 H 4.63493.91253 2.59216 H.89759 3.92658.593476 H 5.34285 1.65343.571636 H 2.75912 4.226533 1.28691 H 6.3139.518781 1.599246 e f C 3.226225.22834 1.582693 C 1.478937 1.436255 1.787765 C 3.438877.961361.94963 C 2.61564 1.753347 1.41755 C 2.7184 1.243489.254175 C 3.64449.855481.66775 C 1.75976.329518.713971 C 2.39425.342455.14372 C 1.535678.86784.27364 C 1.248236.65965.597581 C 2.278713 1.137271 1.118617 C.8417.237592 1.563716 O 4.37536 1.851313 1.36321 O 3.261888 2.9361 1.264171 6
C.56299 1.862986.53823 C.532967 1.974742.336953 C 1.431881.1343 1.91527 C 2.93282 1.532141.184364 C 1.41745.682955.637934 C 1.771254 1.11772.383663 C.716498 2.11235.42394 C.6115 1.932285.7174 C 2.72937 1.115129 2.13922 C 4.2216.714729.486863 C 2.71457 1.767974 1.9262 C 3.964151.64817.215327 C 2.78811 1.195317.19776 C 2.8763 1.182886.365248 C 2.6922.16425.411 C 1.725194.36369.65823 O 2.719263 3.27131.84212 O.88493 2.648795 2.56216 C 1.674293 3.84865.12372 C.7649 1.677173 2.135471 O 3.34968 2.962376 1.31336 O 5.32426 1.44561.56363 O 1.7272 3.169273.692443 O.36821 2.526178 1.524193 C 2.2324 3.27922 1.762667 C.923679 3.73785 2.41764 O 3.6332 2.442435.838728 O 4.188187 1.272994.594168 C 2.319435 2.81522 2.3666 C 4.7386.42463 1.6315 O 3.373585 1.93381 1.133119 O 2.87384 2.532332.59164 C 3.448878 1.427943 2.466971 C 1.765171 3.175688 1.22851 H 3.87894.434766 2.47318 H 1.13859 2.133738 2.543935 H 1.1918.54564 1.61363 H 2.761492 1.45917.879564 H 2.1347 2.66491 1.654822 H.6835.219 2.157116 H 4.379814 2.611695.762837 H 4.18494 2.968683.66218 H.154168 1.52319 1.52616 H 1.271127 2.683735.55837 H.937265.6187 2.726498 H 2.99415 2.592325.397932 H.338147 2.36372 1.366653 H 1.1865 2.952111.714966 H 2.82337 1.56267 3.117845 H 4.919634 1.12595.929474 H 2.78732.448831 1.41484 H.838211.79838 1.94873 H 3.26441 4.1174.553225 H.44122 3.5155 2.64584 H 2.99892 2.778622 1.86117 H.919634 1.647135 2.831832 H 1.129156 4.1794.272437 H.439184.718641 2.198512 H 3.727984 3.255741.47519 H 4.86872 2.348762.239718 H 2.875675 2.63783 1.63221 H 1.614525 2.3188 2.788635 H 1.533698 3.859 2.716449 H 1.51628 3.86983 1.931983 H 2.32412 4.31795 1.8477 H.37228 3.493912 3.25812 H 2.718869 3.78174 2.3226 H 5.67637.94828 1.991517 H 1.244959 2.893784 1.858847 H 4.18121.25945 2.47878 H 2.5868 2.86183 2.831578 H 5.45764.534989 1.18312 H 3.96221.46415 2.495 H 1.586114 2.757242 2.213989 H 2.452322 1.326918 2.92876 H.862539 3.84878.612757 H 4.21165 2.16345 3.3629 H 2.4933 4.223421 1.3161 g h C 3.23784.216766 1.59635 C 1.67758 1.281765 1.765657 C 3.447139.976161.923252 C 2.79594 1.564816.992367 C 2.71113 1.258665.237543 C 3.184236.66865.13866 7
C 1.776718.341741.73656 C 2.455825.494932.226711 C 1.556115.859137.21855 C 1.31836.77571.541452 C 2.296282 1.128728 1.12668 C.943297.119369 1.538196 O 4.372851 1.86894 1.387667 O 3.5949 2.76372 1.217411 C.53866 1.85514.538364 C.529664 2.48447.276382 C 1.48792.143143 1.97369 C 2.89262 1.431779.311843 C 1.415922.697353.63352 C 1.748675.955919.32384 C.691578 2.13266.398138 C.652499 1.923761.732175 C 2.158855 1.58178 2.136895 C 3.917243.569938.72517 C 2.773223 1.718633 1.88951 C 3.811551.786651.453726 C 2.719927 1.1749.2468 C 2.669714 1.28464.19413 C 2.569.249.424367 C 1.65363.42142.575495 O 2.744235 3.336478.755888 O 1.142399 1.779927 3.15241 C 1.65945 3.9225.133263 C.122579 1.69129 2.154656 O 3.432666 2.89524 1.31833 O 4.816949 1.635997.83149 O 1.95461 3.161467.69546 O.17888 2.6377 1.47245 C 2.29159 3.26878 1.762629 C.95287 3.22754 2.32322 O 3.13745 2.46825.81797 O 4.35743 1.4972.699143 C 2.32999 2.829387 2.16111 C 4.78675.2268 1.744464 O 3.368158 1.9123 1.152234 O 2.68412 2.64233.389453 C 3.399857 1.428246 2.496255 C 1.59193 3.24361 1.87248 H 3.817498.423426 2.48845 H 1.39641 1.97751 2.545157 H 1.211541.552774 1.61818 H 2.773944 1.197935.985774 H 2.15519 2.648 1.658717 H.7867.93373 2.152425 H 4.38894 2.631256.789731 H 4.247735 2.72496.59692 H.18257 1.51126 1.52482 H 1.22154 2.783533.15887 H 1.1131.648168 2.738839 H 2.99312 2.492251.59113 H.315726 2.362769 1.36458 H 1.96131 2.925489.72863 H 2.21432 1.485837 3.1396 H 4.8516.947194 1.195966 H 2.1786.43849 1.423392 H.779794.818728 1.7854 H 3.26334 2.5843.92414 H 1.51135 2.671444 3.134834 H 2.24536 2.813465 1.126155 H.36118.695212 2.26548 H 1.126989 4.39768.226481 H.671768 2.414873 2.367128 H 3.798399 3.198257.466327 H 4.56513 2.532657.563479 H 2.92174 2.621494 1.598539 H 1.68296 2.471863 2.681649 H 1.563633 2.988132 2.717133 H 1.483677 4.8597 1.8362 H 2.35553 4.3773 1.85654 H.413249 3.61999 3.1754 H 2.725554 3.8271 2.29712 H 5.66533.69812 2.148837 H 1.254353 2.96437 1.843199 H 4.34846.88931 2.529227 H 2.526455 2.18744 2.813224 H 5.65191.778516 1.353852 H 3.898243.457724 2.548376 H 1.5727 2.835847 2.98531 H 2.39563 1.349278 2.96281 H.653754 3.89666.54884 H 3.96761 2.161826 3.62774 H 1.817726 4.3264 1.136211 8
i C 3.18743.2692 1.618757 C 3.414513.974373.93151 C 2.699755 1.242461.24625 C 1.76795.32351.713565 C 1.529184.865352.17191 C 2.249156 1.121231 1.14653 O 4.337584 1.869287 1.396853 C.511828 1.866839.538333 C 1.47763.137388 1.899389 C 1.427944.69563.62434 C.73747 2.17167.376939 C 2.113266 1.7848 2.139687 C 2.724177 1.754962 1.1374 C 2.694647 1.29276.193952 C 2.54111.87.423894 O 2.81534 3.33368.664967 C 1.6895 3.83.189211 O 3.355737 2.946693 1.33262 O 1.84547 3.173117.669472 C 2.27439 3.28495 1.727523 O 3.1941 2.433327.848 C 2.358846 2.785628 2.56789 O 3.33588 1.968932 1.135442 C 3.389316 1.487877 2.479299 H 3.751127.4292 2.52361 H 1.219274.523499 1.62443 H 2.9197 2.44215 1.69393 H 4.359961 2.621918.787141 H.177557 1.533351 1.53225 H.996234.654523 2.724935 H.36612 2.386444 1.341441 H 2.144421 1.53983 3.13544 H 2.4242.41368 1.424474 H 2.491345 3.76693 1.46663 H 2.114586 2.74317 1.136499 H 1.1493 4.353.377597 H 3.7231 3.25864.491622 H 2.89479 2.635487 1.568838 H 1.567475 3.3432 2.69692 H 2.357635 4.322759 1.748448 H 2.765514 3.75893 2.347376 H 1.2894 2.872263 1.93935 9
H 2.56437 2.5279 2.83858 H 3.9743.527497 2.52843 H 2.38579 1.388883 2.899327 H 3.947449 2.23349 3.3987.6.4.2.2 2 22 24 26 28.4.6 (a).6.4.2 2.2 22 24 26 28.4 (b).6.4.2 2.2 22 24 26 28 1.5 2.5 22 24 26 28 1 (c).4 1.5 (d) 1.5 1.5.6.4.2 2 22 24 26 28.5 2 22 24 26 28.2 1 (e).4 (f) 1
1.5 2 22 24 26 28.5 1 (g).6.4.2 2.2 22 24 26 28.4 (h) 1.5 1.5 2.5 22 24 26 28 1 (i) Figure S2. Calculated ECDs of each conformations of 7R,8R-2 (calculated at the LC-wPBE/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level in MeOH with IEFPCM solvation model. 11
Table S3. Important thermodynamic parameters (a.u.) and Boltzmann distributions of the optimized compound 7R,8R-2 calculated at CAM-B3LYP/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level in MeOH with IEFPCM solvation model. Conformations E+ZPE G % a -1149.973171-115.513587 1.6 b -1149.971854-115.512212.33 c -1149.973336-115.513539 1.46 d -1149.971887-115.512444.31 e -1149.975695-115.516256 14.42 f -1149.9734-115.513755 1.68 g -1149.976998-115.517638 66.49 h -1149.9727-115.512478.41 i -1149.975586-115.516285 13.29 E is the total electronic energy in MeOH at CAM-B3LYP/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level with IEFPCM solvation model, ZPE is the zero point energy in MeOH at B3LYP/6-311++G(2d,p) level with IEFPCM solvation model, and G is the Gibbs free energy by the sum of E and the thermal correction obtained at B3LYP/6-311++G(2d,p) level. %: Boltzmann distributions, using the relative Gibbs free energies as weighting factors. 3 2 1 2 22 24 26 28 1 (a) 3 2 1 2 22 24 26 28 1 (b) 12
3 2 1 2 22 24 26 28 1 (c) 6 5 4 3 2 1 1 2 22 24 26 28 2 (d) 2 1 1 2 22 24 26 28 2 3 4 5 (e) 4 3 2 1 2 1 22 24 26 28 (f) 2 1 1 2 22 24 26 28 2 3 4 (g) 2.5 2 1.5 1.5.5 2 22 24 26 28 (h) 2 1 1 2 22 24 26 28 2 3 4 5 (i) Figure S3. Calculated ECDs of each conformations of 7R,8R-2 (calculated at the 13
CAM-B3LYP/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level in MeOH with IEFPCM solvation model. Figure S4. Calculated and experimental ECDs of 2 and 7R,8R-2 at the CAM-B3LYP/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level in MeOH with IEFPCM solvation model. Table S4. Important thermodynamic parameters (a.u.) and Boltzmann distributions of the optimized compound 7R,8R-2 calculated at WB97XD/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level in MeOH with IEFPCM solvation model. Conformations E+ZPE G % a -115.142381-115.513587 5.79 b -115.1447-115.512212.72 c -115.141879-115.513539 3.4 d -115.1417-115.512444.56 e -115.14282-115.516256 9.4 f -115.142219-115.513755 4.87 g -115.144647-115.517638 63.72 h -115.14881-115.512478 1.18 i -115.142965-115.516285 1.73 E is the total electronic energy in MeOH at WB97XD/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level with IEFPCM solvation model, ZPE is the zero point energy in MeOH at B3LYP/6-311++G(2d,p) level with IEFPCM solvation model, and G is the Gibbs free energy by the sum of E and the thermal correction obtained at B3LYP/6-311++G(2d,p) level. %: Boltzmann 14
distributions, using the relative Gibbs free energies as weighting factors. 5 5 4 4 3 3 2 2 1 1 1 2 22 24 26 28 1 2 25 (a)(b) 5 4 3 2 1 1 2 22 24 26 28 8 6 4 2 2 2 22 24 26 28 (c) (d) 2 1 1 2 22 24 26 28 2 3 4 5 5 4 3 2 1 1 2 22 24 26 28 (e) (f) 2 1 1 2 22 24 26 28 2 3 4 5 5 4 3 2 1 1 2 22 24 26 28 15
(g) (h) 2 1 1 2 22 24 26 28 2 3 4 5 (i) Figure S5. Calculated ECDs of each conformations of 7R,8R-2 (calculated at the WB97XD/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level in MeOH with IEFPCM solvation model. FigureS6. Calculated and experimental ECDs of 2 and 7R,8R-2 at the WB97XD/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) level in MeOH with IEFPCM solvation model. 16
HRESIMS of compound 1 T: FTMS + p ESI Full ms [5.-15.] 399.147 1 9 8 7 Relative Abundance 6 5 4 3 2 4.1441 1 399.36 41.1479 42.1476 399. 399.5 4. 4.5 41. 41.5 42. 42.5 m/z UV spectrum of compound 1 17
IR spectrum of compound 1 3418.4 Transmittance [%] 35 4 45 5 55 6 65 7 2938.39 1614.1 1517.6 1461.32 1338.45 143.47 138.15 1218.22 1115.45 1154.55 136.67 958.84 96.82 81.43 836.17 761.42 79.5 646.65 536.51 35 3 25 2 15 1 5 Wavenumber cm-1 1 H NMR of compound 1 18
13 C NMR and DEPT of compound 1 HSQC of compound 1 19
HMBC of compound 1 1 H 1 H COSY of compound 1 2
NOESY of compound 1 HRESIMS of compound 2 HO 5 3 O OH 9 1' 1 7 O O 3' 5' OH 21
UV spectrum of compound 2 IR spectrum of compound 2 1517.87 1274.33 Transmittance [%] 65 7 75 8 85 9 95 1 15 3366.59 2937.26 2839.9 2644.4 256.68 1862.77 1715.37 165.66 1457.53 1431.62 1371.91 1219.67 1125.31 173.39 131.26 1154.55 195.78 819.31 769.21 856.36 794.7 736.26 956.38 899.74 663.83 68.88 562.57 461.37 35 3 25 2 15 Wavenumber cm-1 1 5 22
1 H NMR of compound 2 13 C NMR and DEPT of compound 2 23
HSQC of compound 2 HMBC of compound 2 24
1 H 1 H COSY of compound 2 NOESY of compound 2 25
HRESIMS of compound 3 UV spectrum of compound 3 26
IR spectrum of compound 3 1517.9 1274.39 131.36 Transmittance [%] 75 8 85 9 95 1 15 3352.86 2934.2 2847.71 2645.57 256.68 1862.97 1713.6 165.33 1458.52 1431.93 1371.6 1218.54 1154.3 1126.9 199.33 173. 896.4 86.3 82.7 792.73 721.42 68.14 658.3 621.11 61.2 561.67 931.54 756.43 953.17 458.89 476.55 35 3 25 2 15 Wavenumber cm-1 1 5 1 H NMR of compound 3 27
13 C NMR and DEPT of compound 3 HSQC of compound 3 28
HMBC of compound 3 1 H 1 H COSY of compound 3 29
NOESY of compound 3 HRESIMS of compound 4 yj T: FTMS + p ESI Full ms [5.-15.] 561.289 1 9 8 7 Relative Abundance 6 5 4 3 562.2123 2 1 577.1829 549.289 563.2153 551.3543 558.27 578.1863 571.2153 575.4272 587.7642 55 555 56 565 57 575 58 585 59 m/z 3
UV spectrum of compound 4 IR spectrum of compound 4 3338.84 Transmittance [%] 2 3 4 5 6 2932.28 1654.55 162.78 1495.99 1515.46 1463.56 1374.6 127.96 127.47 1149.1 1122.7 166.21 132.7 95.9 853.41 86.4 656.81 35 3 25 2 15 Wavenumber cm-1 1 5 31
1 H NMR of compound 4 13 C NMR and DEPT of compound 4 32
HSQC of compound 4 HMBC of compound 4 33
1 H 1 H COSY of compound 4 NOESY of compound 4 34
HRESIMS of compound 5 T: FTMS + p ESI Full ms [5.-15.] 623.2456 1 9 8 7 Relative Abundance 6 5 4 3 624.249 2 1 621.4648 UV spectrum of compound 5 625.2518 626.2549 628.5837 634.723 622 624 626 628 63 632 634 m/z 35
IR spectrum of compound 5 Transmittance [%] 15 11 115 12 125 13 135 14 3366.67 2938.72 2838.44 2877.1 2646.17 257.48 1953.71 1677.82 1598.2 151.6 146.33 1424.56 1214.9 1329.13 1276.71 1234.83 1125.41 132.12 19.79 954.85 912.34 78.84 83.24 738.44 533.1 775.87 646.61 67.27 562.7 35 3 25 2 15 Wavenumber cm-1 1 5 1 H NMR of compound 5 36
13 C NMR and DEPT of compound 5 HSQC of compound 5 37
HMBC of compound 5 1 H 1 H COSY of compound 5 38
NOESY of compound 5 1 H NMR of compound 5 in Acetone-d 6 (4 MHz) 39
HRESIMS of compound 6 UV spectrum of compound 6 4
IR spectrum of compound 6 1125.3 Transmittance [%] 11 115 12 125 13 135 14 145 15 3347.51 2936.85 2838.42 2873.96 1598.47 151.68 1459.97 1424.17 1214.56 1329.48 1276.82 1234.51 133.17 19.32 954.58 912.96 83.6 78.48 776.1 736.37 66.61 532.95 459.7 35 3 25 2 15 Wavenumber cm-1 1 5 1 H NMR of compound 6 41
13 C NMR and DEPT of compound 6 HSQC of compound 6 42
HMBC of compound 6 1 H 1 H COSY of compound 6 43
NOESY of compound 6 1 H NMR of compound 6 in Acetone-d 6 (4 MHz) 44
HRESIMS of compound 7 UV spectrum of compound 7 45
IR spectrum of compound 7 1124.38 Transmittance [%] 115 12 125 13 135 3366.48 2937.23 2873.2 1598.88 151.11 146.6 1424.11 1562.74 1327.74 1277.46 1213.61 131.9 953.23 914.8 831.35 773.79 74.24 74.45 612.13 533.41 46.29 35 3 25 2 15 1 5 Wavenumber cm-1 46
1 H NMR of compound 7 47
13 C NMR and DEPT of compound 7 HSQC of compound 7 48
HMBC of compound 7 1 H 1 H COSY of compound 7 49
NOESY of compound 7 1 H NMR of compound 7 in Acetone-d 6 (4 MHz) 5
HRESIMS of compound 8 T: FTMS + p ESI Full ms [5.-15.] 69.2297 1 9 8 7 Relative Abundance 6 5 4 3 61.2331 2 1 611.236 66.2218 612.2386 615.1379 617.3285 619.315 623.2461 625.235 64 66 68 61 612 614 616 618 62 622 624 m/z UV spectrum of compound 8 51
IR spectrum of compound 8 1124.8 Transmittance [%] 8 85 9 95 3355.87 2923.1 2851.76 1598.73 151.41 1461.61 1213.52 1424.6 1381.9 1328.15 1277.3 1235.86 13.33 953.94 914.49 83.3 774.78 7.19 669.1 649.17 613.18 564.19 532.31 459.59 35 3 25 2 15 Wavenumber cm-1 1 5 1 H NMR of compound 8 52
13 C NMR and DEPT of compound 8 HSQC of compound 8 53
HMBC of compound 8 1 H 1 H COSY of compound 8 54
NOESY of compound 8 1 H NMR of compound 8 in Acetone-d 6 (4 MHz) 55
Chiral HPLC separation profiles of 1a/1b 8a/8b 56