Woodrosin I–Part 1
307 319
tane/EtOAc 94:6 ! 86:14) to give product 42 (71 mg, 71%) as a pale yellow
syrup. [a]2D0 À11.9 (c 2.3, CH2Cl2); IR (KBr): nÄ 3458, 3065, 2969, 2934,
101.63 (d, C-37), 101.39 (d, C-21), 100.81 (d, C-41), 100.25 (d, C-31), 86.05
(d, C-23), 83.61 (d, C-43), 79.85 (d, C-6), 79.54 (d, C-34), 79.01 (d, C-24),
78.50 (d, C-22), 78.47 (d, C-44), 77.47 (d, C-33), 76.26 (d, C-45), 76.07 (d,
C-32), 75.44 (t, 23-OCH2Ph), 75.26 (d, C-25), 74.88 (t, 44-OCH2Ph), 74.75
(t, 24-OCH2Ph), 74.60 (t, 43-OCH2Ph), 74.01 (t, 46-OCH2Ph), 73.78 (26-
OCH2Ph), 73.41 (d, C-42), 69.87 (t, C-46), 69.27 (t, C-26), 68.82 (t, C-36),
67.24 (d, C-35), 41.04 (t, C-39), 35.38 (t, C-7), 34.59 (t, C-3), 34.20 (t, C-5),
34.13 (t, C-52), 33.86 (t, C-55), 32.52 (t, C-10), 28.78 (t, C-54), 25.56 (t, C-8),
24.67 (t, C-53), 24.64 (t, C-4), 23.20 (t, C-9), 14.43 (q, C-11), phenyl signals:
139.18, 139.12, 139.01, 139.00, 138.98, 138.89, 138.20, 128.65, 128.54, 128.52,
128.51, 128.48, 128.45, 128.02, 127.85, 127.69, 126.94.
1
1742, 1498, 1455, 1365, 1142, 1076, 698; H NMR (300 MHz, CD2Cl2): d
7.49 7.00 (m, 25H), 5.91 (ddt, J 17.1, 10.3, 6.6 Hz, 1H), 5.51 (s, 1H), 5.48
(m, 1H), 5.33 (dd, J 7.1, 1.5 Hz, 1H), 5.12 4.96 (m, 4H), 4.89 (AB, J
7.2 Hz, 2H), 4.78 and 4.63 (AB, J 11.1 Hz, 2H), 4.55 (AB, J 12.7 Hz,
2H), 4.44 4.24 (m, 5H), 3.97 (d, J 11.4 Hz, 1H), 3.84 3.92 (m, 2H),
3.82 3.54 (m, 7H), 3.47 (t, J 9.3 Hz, 1H), 3.39 (m, 1H), 3.28 (dt, J 9.7,
5.0 Hz, 1H), 2.72 (brs, OH), 2.45 (hex., J 6.9 Hz, 1H), 2.28 (hex., J
6.9 Hz, 1H), 2.12 2.01 (m, 2H), 1.71 1.24 (m, 3 H), 1.19 (d, J 6.2 Hz,
3H), 1.12 (d, J 6.9 Hz, 3H), 1.03 (d, J 7.0 Hz, 3H), 0.92 0.83 (m, 6H),
0.77 (t, J 7.4 Hz, 3H); 13C NMR (75 MHz, CD2Cl2): d 176.1, 175.6, 139.7,
138.9, 138.8, 138.6, 138.3, 137.8, 129.5, 129.0, 128.7, 128.6, 128.4, 128.0, 127.9,
127.7, 127.6, 126.6, 114.8, 114.1, 102.2, 102.0, 100.9, 98.8, 86.7, 81.7, 81.3, 78.9,
78.6, 77.1, 76.0, 75.9, 75.8, 75.4, 75.3, 75.0, 73.9, 72.6, 71.5, 69.4, 69.1, 67.9,
67.1, 66.2, 41.7, 41.3, 35.2, 34.5, 33.9, 32.4, 27.1, 27.0, 25.3, 24.2, 23.1, 17.9, 17.0,
16.6, 14.3, 11.9, 11.6; MS (EI): m/z (%): 655 (6), 406 (5), 405 (20), 196 (6),
181 (8), 107 (6), 91 (100), 85 (42), 83 (5), 57 (32), 55 (5); elemental analysis
calcd (%) for C74H96O17 (1257.54): C 70.68, H 7.69; found: C 70.56, H 7.78.
Trisaccharide 45: TMSOTf (200 mL of a stock solution, c 0.014m in
CH2Cl2) was added to a solution of imidate 15 (71 mg, 0.14 mmol) and diol
22 (100 mg, 0.12 mmol) in CH2Cl2 (1.2 mL) at À20 C. After stirring for 3 h,
the reaction was quenched with sat. aq. NaHCO3 (5 mL) and the aqueous
phase was extracted with CH2Cl2 (3 Â 10 mL). The combined organic layers
were dried (Na2SO4) and concentrated, and the residue was purified by
flash chromatography (pentane/EtOAc 7:3) to give product 45 (106 mg,
77%) as a colorless solid. [a]D20 À48.0 (c 0.51, CH2Cl2); IR (KAP): nÄ
3431, 3065, 3033, 2929, 2868, 1755, 1640, 1497, 1454, 1370, 1243, 1219, 1097,
Trisaccharides 43 and 44: TMSOTf (200 mL of a stock solution, c 0.014m
in CH2Cl2) was added to a solution of imidate 30 (102 mg, 0.14 mmol) and
diol 22 (100 mg, 0.12 mmol) in CH2Cl2 (1.2 mL) at À208C. After stirring for
3 h, the reaction was quenched with sat. aq. NaHCO3 (5 mL) and extracted
with CH2Cl2 (3 Â 10 mL). The combined organic layers were dried
(Na2SO4) and concentrated, and the residue was purified by flash
chromatography (pentane/EtOAc, 78/22) to give product 43 as a colorless
syrup (149 mg, 90%). 1H NMR (300 MHz, CD2Cl2): d 7.33 7.07 (m,
35H), 5.90 (brs, OH), 5.75 (ddt, J 17.0, 10.3, 6.6 Hz, 1H), 5.64 (ddt, J
17.0, 10.2, 6.7 Hz, 1H), 5.38 (s, 1H), 5.22 5.19 (m, 2H), 4.97 4.30 (m,
18H), 4.15 (dd, J 10.4, 4.8 Hz, 1H), 3.73 (t, J 9 Hz, 1H), 3.64 3.18 (m,
16H), 2.05 1.83 (m, 6H), 1.48 1.16 (m, 16H), 0.80 (t, J 6.6 Hz, 3H);
13C NMR (75 MHz, CD2Cl2): d 172.8, 139.3, 138.9, 138.8, 138.7, 138.6,
138.5, 138.3, 137.9, 129.3, 128.8, 128.7, 128.6, 128.5, 128.4, 128.3, 128.2, 128.1,
128.0, 127.9, 127.8, 126.6, 114.8, 114.7, 104.4, 102.0, 101.3, 100.8, 84.2, 83.3,
81.1, 80.0, 79.8, 79.6, 79.0, 78.2, 76.2, 75.8, 75.3, 75.2, 75.1 (2x), 75.0, 73.8,
73.7, 73.6, 69.3, 69.1, 69.0, 67.3, 35.0, 34.4, 34.3, 33.8, 33.6, 28.7, 25.11, 24.6,
24.5, 23.1, 14.4, 14.3; elemental analysis calcd (%) for C85H102O17 (1395.71):
C 73.15, H 7.37; found: C 73.09, H 7.33.
1030, 915, 750, 699; 1H NMR (600 MHz, [D8]toluene): d 7.75 7.06 (m,
25H, Ph), 5.86 (ddt, J 17.0, 10.1, 6.7 Hz, 1H, H-2), 5.44 (dd, J 9.5,
8.0 Hz, 1H, H-43), 5.29 (dd, J 8.0, 7.1 Hz, 1H, H-42), 5.20 (s, 1H, H-37),
5.13 (ddt, J 17.0, 2.0, 1.8 Hz, 1H, H-1(Z)), 5.07 (ddt, J 10.1, 2.0, 1.2 Hz,
1H, H-1(E)), 5.03 (s, 1H, H-47), 4.93 (d, J 7.0 Hz, 1H, H-41), 4.84 (s, 2H,
23-OCH2Ph), 4.64 (d, J 7.7 Hz, 1H, H-31), 4.53 and 4.66 (AB, J 11.5 Hz,
2H, 24-OCH2Ph), 4.43 and 4.51 (AB, J 12.0 Hz, 2H, 26-OCH2Ph), 4.36
(d, J 7.6 Hz, 1H, H-21), 4.23 (dd, J 10.3, 5.0 Hz, 1H, H-36a), 4.10 (dd,
J 10.3, 5.0 Hz, 1H, H-46a), 3.78 (t, J 9.1 Hz, 1H, H-33), 3.75 (dd, J 8.9,
7.8 Hz, 1H, H-22), 3.70 (d, J 2.4 Hz, 1H, 32-OH), 3.65 (m, 1H, H-6), 3.65
(dd, J 11.1, 4.4 Hz, 1H, H-26a), 3.61 (m (overlapped), 1H, H-24), 3.60 (m
(overlapped), 1H, H-26b), 3.60 (m (overlapped), 1H, H-32), 3.59 (m
(overlapped), 1H, H-44), 3.58 (m (overlapped), 1H, H-23), 3.53 (t, J
10.2 Hz, 1H, H-36b), 3.50 (t, J 10.2 Hz, 1H, H-46b), 3.44 (t, J 9.4 Hz,
1H, H-34), 3.30 (dt, J 10.0, 5.0 Hz, 1H, H-45), 3.23 (m (overlapped), 1H,
H-25), 3.22 (m (overlapped), 1H, H-35), 2.09 (m, 2H, H-3), 1.81 (s, 3H, -
OC(O)CH3), 1.73 (s, 3H, -OC(O)CH3), 1.70 1.50 (m, 8H, H-4,5,7,8),
1.40 1.30 (m, 4H, H-9,10), 0.95 (t, J 7.1 Hz, 3H, H-11); 13C NMR
(150 MHz, [D8]toluene): d 138.98 (d, C-2), 115.09 (t, C-1), 105.09 (d,
C-31), 101.55 (d, C-47), 101.78 (d, C-21), 101.78 (d, C-37), 101.60 (d, C-41),
84.42 (d, C-23), 81.34 (d, C-22), 80.26 (d, C-33), 80.16 (d, C-34), 79.47 (d,
C-6), 79.13 (d, C-24), 78.29 (d, C-44), 76.36 (d, C-32), 75.95 (t, 23-OCH2Ph),
75.35 (d, C-25), 74.74 (t, 24-OCH2Ph), 73.81 (t, 26-OCH2Ph), 73.70 (d,
C-42), 72.79 (d, C-43), 69.26 (t, C-26), 68.99 (t, C-36), 68.90 (t, C-46), 67.37
(d, C-35), 66.53 (d, C-45), 35.38 (t, C-7), 34.54 (t, C-3), 34.19 (t, C-5), 32.51
(t, C-10), 25.43 (t, C-8), 24.80 (t, C-4), 23.21 (t, C-9), 14.44 (q, C-11), acetyl
signals: 169.50 (s), 169.399 (s), 20.53 (q), 20.31 (q), phenyl signals: 138.94,
138.86, 138.34, 138.29, 138.08, 138.29, 138.08, 128.93, 128.57, 128.53, 128.25,
128.19, 126.76, 126.75; MS (EI): m/z (%): 335 (44), 275 (12), 181 (12), 149
(33), 127 (13), 107 (14), 105 (11), 91 (100), 69 (11), 43 (24); elemental
analysis calcd (%) for C68H82O18 (1187.37): C 68.78, H 6.96; found: C 68.72,
H 6.95.
To determine the site of glycosylation unambiguously, this product was
further analyzed after conversion of a small sample into chloroacetate 44
on treatment with chloroacetic acid anhydride and pyridine. Compound 44
1
gave the following spectroscopic properties: H NMR (600 MHz, [D8]tol-
uene, fully resolved signals only): d 7.59 7.05 (m, 35H, Ph), 6.02 (ddt, J
17.0, 10.2, 6.6 Hz, 1H, H-2), 5.70 (ddt, J 17.0, 10.2, 6.7 Hz, 1H, H-56), 5.24
(dq, J 17.0, 1.8 Hz, 1H, H-1(Z)), 5.17 (ddt, J 10.2, 1.8, 1.2 Hz, 1H,
H-1(E)), 5.16 (d, J 7.9 Hz, 1H, H-31), 4.98 (dq, J 17.0, 2.0 Hz, 1H,
H-57(Z)), 4.94 (ddt, J 10.2, 2.0, 1.2 Hz, 1H, H-57(E)), 4.75 (d, J 7.9 Hz,
1H, H-41), 4.31 (d, J 7.2 Hz, 1H, H-21), 4.16 (dd, J 10.4, 5.0 Hz, 1H,
H-36a), 3.98 (t, J 9.1 Hz, 1H, H-33), 3.94 (d, J 4.0 Hz, 2H, H-39), 3.87
(dd, J 7.6 Hz, 1H, H-22), 3.75 (dd, J 12.8, 11.1 Hz, 1H, H-46a), 3.54 (t,
J 9.1 Hz, 1H, H-43), 3.50 (m, 1H, H-45), 3.40 (dd, J 9.5, 9.1 Hz, 1H,
H-44), 2.47 (dt, J 16.2, 7.4 Hz, 1H, H-52a), 2.17 (dt, J 16.2, 7.6 Hz, 1H,
H-52b); 13C NMR (150 MHz, [D8]toluene): d 171.97 (s, C-51), 165.58 (s,
C-38), 139.39 (d, C-2), 138.74 (d, C-56), 115.19 (t, C-1), 114.77 (t, C-57),
Acknowledgement
Generous financial support by the Deutsche Forschungsgemeinschaft
(Leibniz award to A.F.) and by the Fonds der Chemischen Industrie is
gratefully acknowledged. We thank Mrs. K. Radkowski for her assistance at
various stages of this project.
Chem. Eur. J. 2003, 9, No. 1
¹ 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0947-6539/03/0901-0317 $ 20.00+.50/0
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