苯丙素苷Acteoside, Isoacteoside和Ligupurpuroside J的全合成

胡志飞, 徐鹏, 魏炳成, 俞飚

Total Synthesis of Phenylpropanoid Glycosides, Acteoside, Isoacteoside and Ligupurpuroside J^†

HU Zhifei, XU Peng, WEI Bingcheng, YU Biao

Table 3 ¹H and¹³C NMR data of compounds 8—10, 16—20, Acteoside(1), Isoacteoside(4) and Ligupurpuroside J(5)

Compd.	¹H NMR (500 MHz), δ	¹³C NMR (126 MHz), δ
8α^a	7.79 (ddd, J=7.9, 1.4, 0.6 Hz, 1H), 7.46 (dd, J=7.8, 1.4 Hz, 1H), 7.41 (td, J=7.6, 1.4 Hz, 1H), 7.28—7.23 (m, 1H), 6.05 (d, J=1.2 Hz, 1H), 5.60 (dd, J=3.2, 1.2 Hz, 1H), 5.23 (dd, J=10.0, 3.3 Hz, 1H), 5.13—5.06 (m, 3H), 5.00 (d, J=2.0 Hz, 1H), 3.98 (dq, J=9.7, 6.2 Hz, 1H), 3.79—3.68 (m, 2H), 2.20 (s, 3H), 2.14 (s, 3H), 2.07 (s, 3H), 2.06 (s, 3H), 2.00 (s, 3H), 1.54—1.48 (m, 1H), 1.45 (d, J=5.6 Hz, 3H), 1.23 (d, J=6.2 Hz, 3H), 0.95—0.85 (m, 4H)	170.09, 170.05, 169.98, 169.91, 169.79, 163.25, 134.22, 132.23, 130.44, 129.98, 126.88, 125.49, 100.22, 99.36, 90.57, 78.30, 74.07, 73.21, 71.91, 70.86, 70.10, 69.02, 68.55, 67.41, 20.87, 20.82, 20.80, 20.68, 20.60, 18.06, 17.23, 8.99, 8.88, 0.66
8β^a	7.97 (ddd, J=7.9, 1.5, 0.5 Hz, 1H), 7.50 (dd, J=7.8, 1.2 Hz, 1H), 7.46 (td, J=7.6, 1.4 Hz, 1H), 7.36 (ddd, J=7.9, 7.2, 1.5 Hz, 1H), 6.25 (d, J=1.7 Hz, 1H), 5.48—5.41 (m, 2H), 5.14 (dd, J=9.9, 3.3 Hz, 1H), 5.11 (dd, J=3.2, 1.9 Hz, 1H), 5.08 (t, J=9.7 Hz, 1H), 5.02 (d, J=1.9 Hz, 1H), 4.17—4.10 (m, 1H), 3.96 (dq, J=9.4, 6.2 Hz, 1H), 3.81 (t, J=9.6 Hz, 1H), 2.15 (s, 3H), 2.14 (s, 3H), 2.05 (s, 3H), 2.04 (s, 3H), 1.98 (s, 3H), 1.56 (tt, J=8.2, 5.1 Hz, 1H), 1.40 (d, J=6.2 Hz, 3H), 1.22 (d, J=6.3 Hz, 3H), 0.95—0.84 (m, 4H)	169.94, 169.92, 169.89, 169.79, 169.65, 163.80, 134.75, 132.34, 130.94, 130.01, 127.27, 125.20, 100.25, 99.45, 91.31, 78.32, 74.58, 71.46, 70.78, 69.91, 69.58, 69.13, 68.60, 67.42, 20.86, 20.80, 20.78, 20.66, 20.66, 18.20, 17.21, 9.07, 0.71
9^a	6.80 (d, J=8.2 Hz, 1H), 6.76 (d, J=1.8 Hz, 1H), 6.71 (dd, J=8.2, 1.7 Hz, 1H), 6.10—6.00 (m, 2H), 5.43—5.35 (m, 2H), 5.28—5.22(m, 2H), 4.58—4.52 (m, 4H), 4.34 (d, J=3.2 Hz, 2H), 4.30 (d, J=7.7 Hz, 1H), 4.04 (dt, J=15.5, 7.6 Hz, 1H), 4.00—3.81 (m, 3H), 3.75—3.66 (m, 1H), 3.52 (t, J=9.0 Hz, 1H), 3.48—3.44 (m, 1H), 3.43—3.35 (m, 2H), 2.92—2.79 (m, 2H), 2.06 (s, 3H)	171.66, 148.45, 147.19, 133.56, 133.50, 131.07, 121.41, 117.51, 117.46, 115.33, 114.44, 102.71, 76.09, 73.79, 73.39, 71.03, 70.07, 70.05, 70.01, 63.55, 35.56, 20.91
Compd.	¹H NMR (500 MHz), δ	¹³C NMR (126 MHz), δ
10^a	7.62 (d, J=15.8 Hz, 1H), 7.04 (d, J=2.0 Hz, 1H), 7.01 (dd, J=8.3, 2.0 Hz, 1H), 6.83 (d, J=8.3 Hz, 1H), 6.78—6.74 (m, 2H), 6.70 (dd, J=8.2, 1.9 Hz, 1H), 6.31 (d, J=15.9 Hz, 1H), 6.11—5.99 (m, 4H), 5.45—5.35 (m, 4H), 5.32—5.21 (m, 4H), 4.65—4.50 (m, 9H), 4.41 (dd, J=12.3, 2.0 Hz, 1H), 4.32 (d, J=7.7 Hz, 1H), 4.12—4.06 (m, 1H), 3.74—3.67 (m, 1H), 3.59 (t, J=9.0 Hz, 1H), 3.54—3.34 (m, 6H, 3OH), 2.92—2.81 (m, 2H)	168.02, 150.88, 148.54, 148.47, 147.17, 145.97, 133.59, 133.53, 133.03, 132.84, 131.16, 127.24, 123.00, 121.37, 117.98, 117.90, 117.50, 117.45, 115.21, 114.89, 114.38, 113.32, 112.68, 102.91, 75.88, 74.27, 73.56, 71.07, 70.04, 69.94, 69.92, 69.89, 69.67, 63.28, 35.61
16a^a	6.82 (d, J=8.2 Hz, 1H), 6.76 (d, J=1.9 Hz, 1H), 6.73 (dd, J=8.2, 1.9 Hz, 1H), 6.12—6.02 (m, 2H), 5.42 (ddd, J=7.2, 3.1, 1.5 Hz, 1H), 5.38 (ddd, J=7.3, 3.1, 1.5 Hz, 1H), 5.34 (dd, J=3.4, 1.8 Hz, 1H), 5.31 (dd, J=9.9, 3.4 Hz, 1H), 5.28—5.23 (m, 2H), 5.16 (d, J=1.6 Hz, 1H), 5.06 (t, J=9.9 Hz, 1H), 4.61—4.55 (m, 4H), 4.48 (dd, J=12.1, 3.8 Hz, 1H), 4.29 (dd, J=12.1, 1.3 Hz, 1H), 4.23 (d, J=7.7 Hz, 1H), 4.21—4.17 (m, 1H), 4.14—4.08 (m, 1H), 3.67 (dt, J=9.5, 7.5 Hz, 1H), 3.59—3.54 (m, 1H), 3.49—3.40 (m, 3H), 2.88—2.81 (m, 2H), 2.14 (s, 3H), 2.14 (s, 3H), 2.05 (s, 3H), 1.99 (s, 3H), 1.21 (d, J=6.3 Hz, 3H)	171.77, 170.15, 170.02, 169.95, 148.49, 147.19, 133.59, 133.54, 131.26, 121.31, 117.48, 117.46, 115.16, 114.45, 102.88, 98.41, 82.44, 74.03, 73.88, 71.03, 71.00, 70.09, 69.98, 69.71, 69.00, 68.65, 66.97, 63.17, 35.55, 20.94, 20.91, 20.80, 20.73, 17.36
16c^a	6.82 (d, J=8.2 Hz, 1H), 6.77 (d, J=1.9 Hz, 1H), 6.73 (dd, J=8.1, 2.0 Hz, 1H), 6.12—6.02 (m, 2H), 5.42 (dq, J=7.6, 1.6 Hz, 1H), 5.38 (dq, J=7.6, 1.6 Hz, 1H), 5.29—5.24 (m, 3H), 5.13—5.07 (m, 2H), 4.88 (d, J=1.9 Hz, 1H), 4.61—4.55 (m, 4H), 4.32 (d, J=1.8 Hz, 2H), 4.27 (d, J=7.8 Hz, 1H), 4.16—4.07 (m, 2H), 3.76 (s, 1H, OH), 3.69 (dt, J=9.5, 7.6 Hz, 1H), 3.61—3.53 (m, 3H), 3.39 (t, J=8.4 Hz, 1H), 2.91—2.82 (m, 2H), 2.41 (s, 1H, OH), 2.14 (s, 3H), 2.09 (s, 3H), 2.05 (s, 3H), 2.00 (s, 3H), 1.25 (d, J=6.3 Hz, 3H)	170.72, 170.01, 169.82, 148.46, 147.16, 133.56, 133.50, 131.14, 121.28, 117.52, 117.49, 115.08, 114.32, 102.55, 98.91, 80.55, 74.99, 73.53, 72.29, 71.05, 70.64, 70.06, 70.02, 69.92, 68.35, 67.87, 62.46, 35.56, 20.85, 20.82, 20.75, 20.70, 17.34
16d^a	6.82 (d, J=8.2 Hz, 1H), 6.77 (d, J=2.0 Hz, 1H), 6.74 (dd, J=8.2, 2.0 Hz, 1H), 6.12—6.01 (m, 2H), 5.42 (dq, J=9.1, 1.6 Hz, 1H), 5.39 (dq, J=9.1, 1.7 Hz, 1H), 5.33—5.23 (m, 5H), 5.18 (dd, J=10.1, 3.2 Hz, 1H), 5.12—5.06 (m, 3H), 4.95 (d, J=1.9 Hz, 1H), 4.61—4.55 (m, 4H), 4.45—4.35 (m, 3H), 4.30 (dd, J=12.0, 5.0 Hz, 1H), 4.27 (d, J=1.9 Hz, 1H), 4.16—4.08 (m, 1H), 4.04 (dt, J=9.2, 7.8 Hz, 1H), 3.72—3.61 (m, 3H), 3.46—3.35 (m, 2H, 1OH), 2.86 (t, J=8.1 Hz, 2H), 2.13 (s, 3H), 2.12 (s, 3H), 2.09 (s, 3H), 2.04 (s, 3H), 2.00 (s, 3H), 1.98 (s, 3H), 1.97 (s, 3H), 1.24 (d, J=6.4 Hz, 3H), 1.15 (d, J=6.3 Hz, 3H)	171.16, 170.14, 170.11, 169.97, 169.85, 169.76, 169.70, 148.51, 147.23, 133.56, 133.47, 130.64, 121.32, 117.55, 117.50, 115.04, 114.39, 101.37, 99.17, 98.02, 88.90, 75.44, 73.34, 71.30, 71.15, 70.54, 70.04, 69.99, 69.64, 69.49, 68.99, 68.35, 67.99, 66.50, 63.39, 35.52, 20.92, 20.85, 20.84, 20.78, 20.75, 20.64, 17.34, 17.15
17^a	7.62 (d, J=15.9 Hz, 1H), 7.09—7.02 (m, 2H), 6.86 (d, J=8.3 Hz, 1H), 6.81 (d, J=8.2 Hz, 1H), 6.74 (d, J=1.5 Hz, 1H), 6.71 (d, J=8.1 Hz, 1H), 6.22 (d, J=15.9 Hz, 1H), 6.14—6.00 (m, 4H), 5.45—5.36 (m, 4H), 5.33—5.18 (m, 5H), 5.12 (dd, J=10.1, 3.3 Hz, 1H), 5.08 (dd, J=9.5, 8.0 Hz, 1H), 5.04—5.00 (m, 1H), 4.94 (t, J=10.0 Hz, 1H), 4.87 (d, J=1.4 Hz, 1H), 4.67—4.54 (m, 8H), 4.40 (d, J=8.0 Hz, 1H), 4.19 (dd, J=12.4, 4.8 Hz, 1H), 4.15 (dd, J=12.4, 2.9 Hz, 1H), 4.06 (dt, J=9.3, 6.3 Hz, 1H), 3.90 (t, J=9.4 Hz, 1H), 3.83 (dq, J=12.4, 6.2 Hz, 1H), 3.68—3.57 (m, 2H), 2.79 (t, J=6.7 Hz, 2H), 2.09 (s, 3H), 2.07 (s, 3H), 1.99 (s, 3H), 1.94 (s, 3H), 1.84 (s, 3H), 1.03 (d, J=6.2 Hz, 3H)	170.73, 169.97, 169.43, 169.32, 165.47, 151.06, 148.57, 148.40, 147.06, 146.28, 133.67, 133.57, 132.96, 132.72, 131.62, 127.06, 122.94, 121.38, 118.04, 117.94, 117.43, 117.38, 115.32, 114.46, 114.41, 113.37, 112.83, 100.84, 98.87, 80.23, 72.36, 72.09, 70.78, 70.57, 70.14, 70.13, 70.00, 69.93, 69.68, 69.30, 68.52, 67.15, 62.42, 35.55, 20.86, 20.82, 20.67, 20.62, 20.58, 17.53
Compd.	¹H NMR (500 MHz), δ	¹³C NMR (126 MHz), δ
18a^b	7.65 (d, J=15.9 Hz, 1H), 7.23 (d, J=1.9 Hz, 1H), 7.16 (dd, J=8.4, 1.8 Hz, 1H), 6.98 (d, J=8.4 Hz, 1H), 6.91 (d, J=1.9 Hz, 1H), 6.87 (d, J=8.2 Hz, 1H), 6.79 (dd, J=8.2, 1.9 Hz, 1H), 6.39 (d, J=15.9 Hz, 1H), 6.13—6.01 (m, 4H), 5.46—5.35 (m, 4H), 5.29—5.21 (m, 4H), 5.20 (d, J=1.6 Hz, 1H), 4.92 (t, J=9.5 Hz, 1H), 4.64—4.60 (m, 4H), 4.58—4.52 (m, 4H), 4.38 (d, J=7.9 Hz, 1H), 4.08 (dt, J=9.7, 7.2 Hz, 1H), 3.91 (dd, J=3.2, 1.8 Hz, 1H), 3.82 (t, J=9.2 Hz, 1H), 3.79—3.73 (m, 1H), 3.65—3.50 (m, 5H), 3.39 (dd, J=9.1, 8.0 Hz, 1H), 3.31—3.26 (m, 1H), 2.91—2.83 (m, 2H), 1.09 (d, J = 6.2 Hz, 3H)	166.57, 150.96, 148.55, 148.45, 146.98, 145.91, 133.78, 133.72, 133.34, 133.11, 132.21, 127.50, 122.89, 121.41, 116.41, 116.33, 116.06, 116.02, 115.40, 114.80, 114.68, 113.43, 112.91, 102.79, 101.55, 80.06, 74.78, 74.62, 72.34, 70.92, 70.65, 70.50, 69.92, 69.69, 69.57, 69.32, 69.28, 68.97, 60.98, 35.24, 17.04
18b^b	7.59 (d, J=15.9 Hz, 1H), 7.16 (d, J=2.0 Hz, 1H), 7.03 (dd, J=8.4, 2.0 Hz, 1H), 6.92 (d, J=8.4 Hz, 1H), 6.84 (s, 1H), 6.72—6.69 (m, 2H), 6.38 (d, J=16.0 Hz, 1H), 6.12—5.97 (m, 4H), 5.46—5.33 (m, 4H), 5.29—5.17 (m, 5H), 4.61—4.55 (m, 4H), 4.51 (dd, J=11.8, 2.3 Hz, 1H), 4.50—4.41 (m, 4H), 4.37 (dd, J=12.0, 6.6 Hz, 1H), 4.34 (d, J=7.9 Hz, 1H), 4.05—3.92 (m, 3H), 3.75 (ddd, J=9.9, 8.1, 6.9 Hz, 1H), 3.70 (dd, J=9.5, 3.4 Hz, 1H), 3.60—3.55 (m, 1H), 3.53 (t, J=8.9 Hz, 1H), 3.43—3.37 (m, 2H), 3.35—3.31 (m, 1H), 2.88—2.77 (m, 2H), 1.25 (d, J=6.2 Hz, 3H)	167.33, 150.79, 148.51, 148.29, 146.87, 145.16, 133.72, 133.67, 133.36, 133.11, 131.84, 127.40, 122.84, 121.31, 116.43, 116.31, 116.07, 116.05, 115.09, 114.90, 114.30, 113.21, 112.41, 103.03, 101.32, 82.54, 74.28, 73.92, 72.54, 70.92, 70.85, 70.80, 69.71, 69.50, 69.43, 69.21, 69.15, 68.61, 63.33, 35.44, 16.47
19a^a	7.68 (d, J=15.9 Hz, 1H), 7.11—7.06 (m, 2H), 6.87 (d, J=8.9 Hz, 1H), 6.80 (d, J=8.2 Hz, 1H), 6.75 (d, J=1.9 Hz, 1H), 6.72 (dd, J=8.1, 2.0 Hz, 1H), 6.36 (d, J=15.9 Hz, 1H), 6.13—6.01 (m, 4H), 5.45 (td, J=3.1, 1.5 Hz, 1H), 5.43—5.40 (m, 2H), 5.38 (ddd, J=6.3, 3.2, 1.6 Hz, 1H), 5.35—5.28 (m, 4H), 5.26 (ddd, J=4.3, 2.8, 1.4 Hz, 1H), 5.24 (ddd, J=4.3, 2.8, 1.3 Hz, 1H), 5.17 (d, J=1.6 Hz, 1H), 5.06 (t, J=9.9 Hz, 1H), 4.73 (dd, J=12.0, 2.6 Hz, 1H), 4.66—4.62 (m, 4H), 4.59—4.54 (m, 4H), 4.33 (d, J=12.0 Hz, 1H), 4.28—4.21 (m, 2H), 4.14 (dt, J = 9.6, 6.7 Hz, 1H), 3.67 (dt, J=9.5, 7.5 Hz, 1H), 3.62—3.57 (m, 1H), 3.50—3.44 (m, 3H), 3.42 (s, 1H, OH), 2.89—2.81 (m, 2H), 2.23 (d, J=2.2 Hz, 1H, OH), 2.14 (s, 3H), 2.04 (s, 3H), 1.98 (s, 3H), 1.21 (d, J=6.3 Hz, 3H)	170.11, 170.02, 169.97, 168.04, 150.88, 148.55, 148.49, 147.18, 146.09, 133.58, 133.53, 133.01, 132.82, 131.24, 127.31, 123.05, 121.30, 117.99, 117.91, 117.48, 117.45, 115.12, 114.85, 114.42, 113.35, 112.70, 103.01, 98.34, 81.83, 74.49, 74.07, 71.07, 71.06, 70.07, 69.96, 69.94, 69.73, 69.70, 69.04, 68.48, 66.86, 62.93, 35.57, 20.91, 20.81, 20.73, 17.34
19b^a	7.64 (d, J=15.9 Hz, 1H), 7.07— 7.03 (m, 2H), 6.86 (d, J=8.1 Hz, 1H), 6.80 (d, J=8.2 Hz, 1H), 6.78 (d, J=2.0 Hz, 1H), 6.74 (dd, J=8.2, 2.0 Hz, 1H), 6.32 (d, J=15.9 Hz, 1H), 6.12—6.01 (m, 4H), 5.47—5.22 (m, 11H), 5.07 (t, J=9.7 Hz, 1H), 4.73 (dd, J=12.4, 3.6 Hz, 1H), 4.67—4.54 (m, 8H), 4.43 (d, J=7.7 Hz, 1H), 4.33—4.26 (m, 2H), 4.08 (dt, J=9.1, 7.8 Hz, 1H), 3.73—3.66 (m, 2H), 3.55 (dd, J=9.2, 7.7 Hz, 1H), 3.43 (ddd, J=9.7, 3.6, 2.1 Hz, 1H), 3.35 (t, J=9.4 Hz, 1H), 2.88 (t, J=8.1 Hz, 2H), 2.14 (s, 3H), 2.02 (s, 3H), 2.00 (s, 3H), 1.17 (d, J =6.3 Hz, 3H)	170.43, 170.41, 170.00, 168.43, 150.92, 148.52, 148.48, 147.16, 146.31, 133.56, 133.48, 132.97, 132.80, 130.80, 127.14, 123.09, 121.30, 118.06, 117.97, 117.56, 117.50, 115.02, 114.64, 114.34, 113.26, 112.50, 101.87, 97.57, 76.89, 74.16, 71.32, 71.10, 70.03, 69.95, 69.88, 69.86, 69.74, 69.68, 69.27, 66.45, 62.92, 35.64, 21.00, 20.85, 20.82, 17.25
20a^a	7.67 (d, J=15.9 Hz, 1H), 7.10—7.05 (m, 2H), 6.86 (d, J=8.3 Hz, 1H), 6.79 (d, J=8.2 Hz, 1H), 6.75 (d, J=2.0 Hz, 1H), 6.72 (dd, J=8.2, 2.0 Hz, 1H), 6.36 (d, J=15.9 Hz, 1H), 6.13—6.00 (m, 4H), 5.47—5.35 (m, 5H), 5.32—5.22 (m, 5H), 5.20 (dd, J=10.0, 3.3 Hz, 1H), 5.12—5.09 (m, 2H), 5.07 (t, J=9.9 Hz, 1H), 4.95 (d, J=2.0 Hz, 1H), 4.69—4.61 (m, 5H), 4.59—4.54 (m, 4H), 4.38 (dd, J=12.3, 2.0 Hz, 1H), 4.24 (d, J=7.7 Hz, 1H), 4.21—4.15 (m, 1H),	170.25, 170.01, 169.95, 169.90, 169.78, 167.89, 150.75, 148.49, 148.43, 147.09, 145.94, 133.58, 133.52, 133.01, 132.85, 131.26, 127.35, 123.04, 121.29, 118.02, 117.94, 117.54, 117.50, 114.99, 114.31, 113.26, 112.55, 103.01, 99.26, 98.41, 82.22, 79.05, 74.38, 73.97, 71.40, 71.09, 70.89,
Compd.	¹H NMR (500 MHz), δ	¹³C NMR (126 MHz), δ
20a^a	4.13 (dt, J=9.5, 6.8 Hz, 1H), 3.97 (dq, J=9.9, 6.3 Hz, 1H), 3.70—3.63 (m, 2H), 3.60—3.45 (m, 4H), 2.88—2.81 (m, 2H), 2.13 (s, 3H), 2.10 (s, 3H), 2.04 (s, 3H), 2.03 (s, 3H), 1.97 (s, 3H), 1.35 (d, J=6.2 Hz, 3H), 1.21 (d, J=6.2 Hz, 3H)	70.07, 70.03, 69.93, 69.89, 69.87, 69.68,68.68, 68.48, 67.39, 67.27, 62.97, 35.58, 20.92, 20.89, 20.81, 20.76, 20.69, 18.05, 17.23
20b^a	7.65 (d, J=15.9 Hz, 1H), 7.08—7.03 (m, 2H), 6.87 (d, J=8.1 Hz, 1H), 6.82 (d, J=1.7 Hz, 1H), 6.81—6.76 (m, 2H), 6.32 (d, J=15.9 Hz, 1H), 6.13—6.00 (m, 4H), 5.47—5.22 (m, 10H), 5.19—5.15 (m, 2H), 5.13 (dd, J=3.3, 1.9 Hz, 1H), 5.04 (t, J=9.9 Hz, 1H), 4.96 (d, J=2.0 Hz, 1H), 4.74 (dd, J=12.4, 3.5 Hz, 1H), 4.67—4.52 (m, 8H), 4.44 (d, J=7.7 Hz, 1H), 4.29 (dd, J=12.4, 2.0 Hz, 1H), 4.27—4.22 (m, 1H), 4.12—4.05 (m, 1H), 3.96—3.88 (m, 1H), 3.76—3.63 (m, 3H), 3.52 (dd, J=9.2, 7.7 Hz, 1H), 3.48—3.42 (m, 2H), 3.36 (td, J=9.3, 3.5 Hz, 1H, OH), 3.04 (d, J=3.0 Hz, 1H, OH), 2.90 (t, J=8.0 Hz, 2H), 2.12 (s, 3H), 2.10 (s, 3H), 2.05 (s, 3H), 1.96 (s, 3H), 1.95 (s, 3H), 1.32 (d, J=6.2 Hz, 3H), 1.16 (d, J=6.3 Hz, 3H)	170.54, 170.16, 169.98, 169.94, 169.66, 168.40, 150.89, 148.52, 148.47, 147.06, 146.26, 133.64, 133.55, 132.99, 132.81, 130.98, 127.18, 123.07, 121.49, 118.06, 117.97, 117.51, 117.42, 115.08, 114.70, 114.39, 113.28, 112.51, 101.97, 99.31, 97.69, 79.08, 77.38, 74.10, 71.67, 71.46, 70.78, 70.08, 70.03, 69.89, 69.87, 69.81, 69.69, 68.70, 67.31, 67.17, 62.92, 35.77, 20.95, 20.88, 20.79, 20.71, 20.65, 17.96, 17.23
Acteoside(1)^b	7.59 (d, J=15.9 Hz, 1H), 7.05 (d, J=1.9 Hz, 1H), 6.96 (dd, J=8.2, 1.9 Hz, 1H), 6.78 (d, J=8.2 Hz, 1H), 6.70 (d, J=1.9 Hz, 1H), 6.67 (d, J=8.0 Hz, 1H), 6.57 (dd, J=8.0, 1.9 Hz, 1H), 6.27 (d, J=15.9 Hz, 1H), 5.19 (d, J=1.3 Hz, 1H), 4.92 (t, J=9.5 Hz, 1H), 4.38 (d, J=7.9 Hz, 1H), 4.08—4.02 (m, 1H), 3.92 (dd, J=3.0, 1.7 Hz, 1H), 3.82 (t, J=9.2 Hz, 1H), 3.76—3.69 (m, 1H), 3.65—3.50 (m, 5H), 3.39 (dd, J=8.9, 8.1 Hz, 1H), 3.30—3.26 (m, 1H), 2.85—2.76 (m, 2H), 1.09 (d, J=6.2 Hz, 3H)	168.27, 149.79, 148.00, 146.84, 146.14, 144.68, 131.46, 127.66, 123.19, 121.24, 117.10, 116.50, 116.29, 115.21, 114.70, 104.22, 103.03, 81.63, 76.22, 76.06, 73.80, 72.36, 72.26, 72.06, 70.59, 70.42, 62.37, 36.58, 18.45
Isoacteoside (4)^b	7.55 (d, J=15.9 Hz, 1H), 7.02 (d, J=1.6 Hz, 1H), 6.88 (dd, J=8.1, 1.7 Hz, 1H), 6.76 (d, J=8.2 Hz, 1H), 6.66 (d, J=1.6 Hz, 1H), 6.62 (d, J=8.0 Hz, 1H), 6.52 (dd, J=8.0, 1.7 Hz, 1H), 6.28 (d, J=15.9 Hz, 1H), 5.17 (s, 1H), 4.48 (dd, J=11.8, 1.8 Hz, 1H), 4.34 (dd, J=11.9, 5.6 Hz, 1H), 4.32 (d, J=7.9 Hz, 1H), 4.03—3.91 (m, 3H), 3.73—3.66 (m, 2H), 3.55—3.49 (m, 2H), 3.42—3.36 (m, 2H), 3.34—3.30 (m, 1H), 2.82—2.71 (m, 2H), 1.23 (d, J=6.2 Hz, 3H)	169.1, 149.6, 147.2, 146.8, 146.1, 144.6, 131.3, 127.6, 123.1, 121.2, 117.0, 116.5, 116.3, 115.0, 114.7, 104.3, 102.7, 83.8, 75.7, 75.4, 73.9, 72.4, 72.3, 72.2, 70.3, 70.0, 64.6, 36.7, 17.8
Ligupurpuroside J (5)^b	7.56 (d, J=15.9 Hz, 1H), 7.03 (d, J=1.9 Hz, 1H), 6.89 (dd, J=8.2, 1.9 Hz, 1H), 6.76 (d, J=8.2 Hz, 1H), 6.66 (d, J=1.9 Hz, 1H), 6.62 (d, J=8.0 Hz, 1H), 6.53 (dd, J=8.1, 1.9 Hz, 1H), 6.29 (d, J=15.9 Hz, 1H), 5.19 (s, 2H), 4.49 (dd, J=11.8, 1.8 Hz, 1H), 4.35—4.30 (m, 2H), 4.11 (dq, J=12.5, 6.2 Hz, 1H), 3.98—3.91 (m, 2H), 3.90—3.86 (m, 1H), 3.83 (dd, J=9.2, 3.3 Hz, 1H), 3.74—3.66 (m, 2H), 3.59 (dd, J=9.5, 3.3 Hz, 1H), 3.56—3.50 (m, 3H), 3.41—3.35 (m, 2H), 2.81—2.72 (m, 2H), 1.27 (d, J=6.2 Hz, 3H), 1.24 (d, J=6.2 Hz, 3H)	169.1, 149.6, 147.2, 146.8, 146.1, 144.6, 131.3, 127.6, 123.1, 121.2, 117.0, 116.5, 116.3, 115.0, 114.8, 104.4, 103.2, 102.4, 83.4, 81.1, 75.8, 75.4, 73.8, 73.0, 72.9, 72.4, 72.3, 70.4, 70.3, 68.4, 64.6, 36.7, 18.5, 17.8