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79955565428
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16 The peaks of hydrolysates were detected at 14.11 min for d-glucose and 8.21 min d-xylose, respectively. The retention times of the authentic samples (Sigma-Aldrich), after being treated in a similar manner, were 14.11 (d-glucose), 14.24 (l-glucose), 8.21 (d-xylose), and 8.66 min (l-xylose).
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3-MeOH (9:1), to afford aglycones 2a (1.0 mg) and 3a (2.0 mg), respectively.
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Preparation of the (R)- and (S)-MTPA ester derivatives of compound 3a: Two portions (each 0.4 mg) of 3a were treated with either (S)-(+)-R- or (R)- (-)-R-methoxy-R(trifluoromethyl)phenylacetyl chloride (5.0 μL) in anhydrous pyridine (50.0 μL) at room temperature overnight. The reaction mixtures were purified over small silica gel columns with n-hexane-EtOAc (8:1) as the elution solvent, to afford the (R)- and (S)-MTPA ester derivatives of 3a, respectively. R-MTPA ester of 3a: δ 1.89 (1H, d, J = 14.0 Hz, H-2 ax), 1.26 (1H, d, J = 14.0 Hz, H-2 eq), 5.22 (1H, m, H-3), 1.83 (1H, m, H-4 ax), 1.53 (1H, m, H-4 eq), 1.29 (1H, m, H-5), 1.84 (1H, m, H-7 ax), 1.53 (1H, m, H-7 eq), 1.71 (1H, m, H-8 ax), 1.64 (1H, m, H-8 eq), 5.01 (1H, m, H-9), 1.25 (3H, J = 9.0 Hz, H-10), 1.84 (3H, s, H-11), 1.53 (3H, s, H-12), 0.85 (3H, J = 6.5 Hz, H-13). S-MTPA ester of 3a: δ 1.90 (1H, J = 14.0 Hz, H-2 ax), 1.33 (1H, d, J = 14.0 Hz, H-2 eq), 5.17 (1H, m, H-3), 1.67 (1H, m, H-4 ax), 1.41 (1H, m, H-4 eq), 1.30 (1H, m, H-5), 1.84 (1H, m, H-7 ax), 1.33 (1H, m, H-7 eq), 1.44 (1H, m, H-8 ax), 1.44 (1H, m, H-8 eq), 4.97 (1H, m, H-9), 1.31 (3H, J = 9.0 Hz, H-10), 0.79 (3H, s, H-11), 0.72 (3H, s, H-12), 0.62 (3H, J = 6.5 Hz, H-13).
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