1. Studies on the Constituents of Cimicifuga Species. XX. Absolute Stereostructures of Cimicifugoside and Actein from Cimicifu simplex WORMSK.
2. 2) 1H-NMR spectra of 1 (in pyridine-d5) δ: 1.14, 1.53 (each 1H, H-1), 1.91, 2.28 (each 1H, H-2), 3.47 (1H, dd, J=4.3, 11.6 Hz, 3-H), 1.27 (1H, H-5), 0.72, 1.49 (each 1H, H-6), 0.95, 1.25 (each 1H, H-7), 1.62 (1H, dd, J=5.2, 11.6 Hz, H-8), 1.17 (1H, dd, J=3.8, 16.2 Hz, H-11), 2.72 (1H, dd, J=8.9, 16.2 Hz, H-11), 5.08 (1H, dd, J=3.8, 8.9 Hz, H-12), 1.83 (1H, dd, J=5.2, 13.5 Hz, H-15), 2.00 (1H, dd, J=8.2, 13.5 Hz, H-15), 4.81 (1H, ddd, J=5.2, 8.2, 8.3 Hz, H-16), 2.14 (1H, dd, J=8.3, 11.0 Hz, H-17), 1.25 (3H, s, H-18), 0.21, 0.58 (each 1H, d, J=4.3 Hz, H-19), 2.01 (1H, m, H-20), 0.98 (3H, d, J=6.1 Hz, H-21), 2.27 (1H, dd, J=13.2, 14.6 Hz, H-22), 2.48 (1H, dd, J=3.2, 14.6 Hz, H-22), 0.86 (3H, s, H-28), 1.33 (3H, s, H-29), 1.02 (3H, s, H-30), 2.14 (3H, s, Ac), 4.86 (1H, d, J=7.3 Hz, xyl H-1), 4.04 (1H, dd, J=7.3, 8.7 Hz, xyl H-2), 4.17 (1H, dd, J=8.7, 8.7 Hz, xyl H-3), 4.25 (1H, m, xyl H-4), 3.75 (1H, dd, J=10.3, 11.1 Hz, xyl H-5), 4.37 (1H, dd, J=5.0, 11.1 Hz, xyl H-5). 13C-NMR spectra of 1 (in pyridine-d5) δ: 32.0 (C-1), 30.0 (C-2), 88.1 (C-3), 41.3 (C-4), 47.1 (C-5), 20.5 (C-6), 25.7 (C-7), 46.0 (C-8), 20.3 (C-9), 27.0 (C-10), 36.5 (C-11), 76.7 (C-12), 48.7 (C-13), 48.4 (C-14), 43.9 (C-15), 80.4 (C-16), 53.7 (C-17), 13.4 (C-18), 29.7 (C-19), 26.9 (C-20), 22.1 (C-21), 38.7 (C-22), 173.5 (C-23), 19.6 (C-28), 25.8 (C-29), 15.4 (C-30), 21.5 (Ac), 170.5 (Ac), 107.6 (xyl C-1), 75.6 (xyl C-2), 78.7 (xyl C-3), 71.3 (xyl C-4), 67.2 (xyl C-5).
3. 3) 1H-NMR spectra of 2 (in pyridine-d5) δ: 1.14, 1.58 (each 1H, H-1), 1.89, 2.27 (each 1H, H-2), 3.45 (1H, dd, J=4.0, 11.6 Hz, 3-H), 1.20 (1H, dd, J=5.5, 12.6 Hz, H-5), 1.57, 1.87 (each 1H, H-6), 5.12 (1H, br d, J=6.8 Hz, H-7), 1.26 (1H, dd, J=3.8, 16.0 Hz, H-11), 2.92 (1H, dd, J=9.2, 16.0 Hz, H-11), 5.20 (1H, dd, J=3.8, 9.2 Hz, H-12), 2.15 (1H, dd, J=3.9, 12.9 Hz, H-15), 2.25 (1H, dd, J=8.5, 12.9 Hz, H-15), 4.91 (1H, ddd, J=3.9, 8.1, 8.5 Hz, H-16), 2.14 (1H, dd, J=8.1, 11.2 Hz, H-17), 1.28 (3H, s, H-18), 0.52, 1.04 (each 1H, d, J=4.3 Hz, H-19), 2.02 (1H, m, H-20), 0.98 (3H, d, J=6.4 Hz, H-21), 2.29 (1H, dd, J=13.3, 14.6 Hz, H-22), 2.48 (1H, dd, J=3.2, 14.6 Hz, H-22), 1.06 (3H, s, H-28), 1.34 (3H, s, H-29), 1.03 (3H, s, H-30), 2.14 (3H, s, Ac), 4.85 (1H, d, J=7.6 Hz, xyl H-1), 4.05 (1H, dd, J=7.6, 8.7 Hz, xyl H-2), 4.17 (1H, dd, J=8.7, 8.7 Hz, xyl H-3), 4.25 (1H, m, xyl H-4), 3.75 (1H, dd, J=10.2, 11.2 Hz, xyl H-5), 4.36 (1H, dd, J=5.2, 11.2 Hz, xyl H-5). 13C-NMR spectra of 2 (in pyridine-d5) δ: 30.3 (C-1), 29.6 (C-2), 87.8 (C-3), 40.5 (C-4), 42.4 (C-5), 21.9 (C-6), 114.5 (C-7), 147.2 (C-8), 21.4 (C-9), 28.5 (C-10), 36.4 (C-11), 76.3 (C-12), 47.9 (C-13), 50.9 (C-14), 42.8 (C-15), 80.5 (C-16), 54.1 (C-17), 14.8 (C-18), 29.1 (C-19), 26.9 (C-20), 22.0 (C-21), 38.6 (C-22), 173.4 (C-23), 26.8 (C-28), 25.8 (C-29), 14.3 (C-30), 21.5 (Ac), 170.6 (Ac), 107.5 (xyl C-1), 75.7 (xyl C-2), 78.7 (xyl C-3), 71.3 (xyl C-4), 67.2 (xyl C-5).
4. Peculiar side-chain fission of steroidal glycosides