SUPPLEMENTARY MATERIAL
Enantiomeric separation of angular-type pyranocoumarins from
Peucedani Radix using AD-RH chiral column
Yue-Lin Song a,b, Wang-Hui Jing a, Peng-Fei Tu b,c and Yi-Tao Wang a*
a
State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese
Medical Sciences, University of Macau, Macao SAR, China.
b
Modern Research Center for Traditional Chinese Medicine, Beijing University of
Chinese Medicine, Beijing 100029, P. R. China
c
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical
Sciences, Peking University, Beijing 100191, P.R. China
*
To whom correspondence should be addressed: Prof. Yi-Tao Wang, E-mail:
ytwang@umac.mo.
Abstract
Enantiomers and diastereoisomers of angular-type pyranocoumarins are widely
distributed in Peucedani Radix (Chinese name: Qian-hu), eliciting distinct activities
during action in vitro and in vivo. Our ongoing investigations on this type of
coumarins afforded eight pairs of enantiomers (1a and 1b, 2a and 2b, 3a and 3b, 4a
and 4b, 5a and 5b, 6a and 6b, 7a and 7b, 8a and 8b) through enantiomeric separation
of trans-3′-angeloylkhellactone (1), trans-3′-acetyl-4′-isobutyrylkhellactone (2),
trans-3′-acetyl-4′-angeloylkhellactone (3) 3′-angeloyloxy-4′-oxo-3′,4′-dihydroseselin
(4), cis-3′-acetyl-4′-angeloylkhellactone (5), cis-3′-isovaleryl-4′-acetylkhellactone (6),
cis-3′-angeloyl-4′-isovalerylkhellactone (7), and cis-3′,4′-diisovalerylkhellactone (8)
using semi-preparative CHIRALPAK AD-RH column, respectively. All the
compounds 1-8 were enantioseparated for the first time, while the absolute configurations
of compounds 2a, 2b, 6a and 8b were also firstly characterized.
Keywords:
Angular-type
pyranocoumarins;
separation; Chiral column; Peucedani Radix
Enantiomers;
Enantiomeric
The NMR spectroscopic data and MS spectral values of compounds 2-4
Compound 2 Positive ESI-MS m/z: 413[M+K]+, 397[M+Na]+, 375[M+H]+,
287[M+H-C3H7COOH]+ and 227 [M+H-CH3COOH-C3H7COOH]+. 1H-NMR (600
MHz, CDCl3) δ: 6.25 (1H, d, J = 9.5 Hz, 3-H), 7.62 (1H, d, J = 9.5 Hz, 4-H), 7.38 (1H,
d, J = 8.6 Hz, 5-H), 6.84 (1H, d, J = 8.6 Hz, 6-H), 5.30 (1H, d, J = 4.1 Hz, 3′-H), 6.18
(1H, d, J = 4.1 Hz, 4′-H),1.39 (3H, s, 5′-H), 1.46 (3H, s, 6′-H), 2.12 (3H, s, 2′′-H),
1.23,1.20 (each 3H, d, J = 6.6 Hz, 3′′′, 4′′′-H).
Compound 3 Positive ESI-MS m/z: 425[M+K]+, 409[M+Na]+, 387[M+H]+,
327[M+H-C4H7COOH]+ and 227 [M+H-C4H7COOH-CH3COOH]+. 1H-NMR (600
MHz, CDCl3) δ: 6.24 (1H, d, J = 9.5 Hz, 3-H), 7.61 (1H, d, J = 9.5 Hz, 4-H), 7.38 (1H,
d, J = 8.6 Hz, 5-H), 6.29 (1H, d, J = 8.6 Hz, 6-H), 5.33 (1H, d, J = 3.6 Hz, 3′-H), 5.28
(1H, d, J = 3.6 Hz, 4′-H), 1.40 (3H, s, 5′-H), 1.47 (3H, s, 6′-H), 2.12 (3H, s, 2′′-H),
6.08 (1H, q, J = 7.2 Hz, 3′′′-H), 2.02 (3H, d, J = 7.2 Hz, 4′′′-H), 1.86 (3H, s, 5′′′-H).
Compound 4 Positive ESI-MS m/z: 381[M+K]+, 365[M+Na]+, 343[M+H]+, and
243 [M+H-C4H7COOH]+. 1H-NMR (600 MHz, CDCl3) δ:
6.33 (1H, d, J = 9.6 Hz,
3-H), 7.61 (1H, d, J = 9.6 Hz, 4-H), 7.56 (1H, d, J = 8.6 Hz, 5-H), 6.89 (1H, d, J = 8.6
Hz, 6-H), 5.68 (1H, d, J = 3.6 Hz, 3′-H), 1.43 (3H, s, 5′-H), 1.60 (3H, s, 6′-H), 6.22
(1H, q, J = 7.2 Hz, 3′′-H), 2.05 (3H, d, J = 7.2 Hz, 4′′-H), 1.98 (3H, s, 5′′-H).
Figure S1 Typical total ion current (TIC) chromatograms of 1-8 (A-H) on
CHIRALPAK AD-RH analytical-type column.