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Dihydroisocoumarin Constituents from the Leaves of Hydrangea Macrophylla Var

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Dihydroisocoumarin Constituents from the Leaves of Hydrangea Macrophylla Var March 1999 Chem. Pharm. Bull. 47(3) 383—387 (1999) 383 Dihydroisocoumarin Constituents from the Leaves of Hydrangea macrophylla var. thunbergii (2).1): Absolute Stereostructures of Hydrangenol, Thunberginol I, and Phyllodulcin Glycosides and Isomerization Reaction at the 3-Positions of Phyllodulcin and Its Glycosides Masayuki YOSHIKAWA,* Tomohiko UEDA, Hiroshi SHIMODA, Toshiyuki MURAKAMI, Johji YAMAHARA, and Hisashi MATSUDA Kyoto Pharmaceutical University, 5 Nakauchi-cho, Misasagi, Yamashina-ku, Kyoto 607–8414, Japan. Received October 15, 1998; accepted December 10, 1998 Following the characterization of 3S-phyllodulcin, 3R- and 3S-phyllodulcin 39-O-glucosides, and 3R- and 3S- thunberginol H 8-O-glucosides, six new dihydroisocoumarin glycosides, 3R- and 3S-hydrangenol 49-O-apiosylglu- cosides, 3R- and 3S-thunberginol I 49-O-glucosides, thunberginol I 8-O-glucoside, and 3S-phyllodulcin 8-O-glu- coside, were isolated from the dried leaves of Hydrangea macrophylla var. thunbergii and their structures were determined on the basis of chemical and physicochemical evidence. In addition, isomerization reaction at the 3- positions of phyllodulcin and its glycosides was examined. Key words thunberginol I glycoside; hydrangenol glycoside; Hydrangea macrophylla var. thunbergii; dihydroisocoumarin gly- coside; dihydroisocoumarin 3-isomerization; Hydrangeae Dulcis Folium In the course of our studies on bioactive constituents of 8.6 Hz, 29, 69-H), 10.92 (1H, br s, 8-OH)], a b-D-glucopyra- 2) 3) natural medicines and medicinal foodstuffs, we have re- nosyl moiety [d 4.85 (d, J57.5 Hz, 10-H)], and b-D-apiofura- ported the isolation and structure elucidation of antiallergic nosyl moiety [d 4.83 (d, J53.0 Hz, 1--H)]. Comparison of and antimicrobial principles such as thunberginols A,4) B,4) the NMR data for 1 with those of hydrangenol (7)5) and 3R- C,5) D,5) E,5) and F,4) thunberginol G 39-O-glucoside,5) and hydrangenol 49-O-glucoside (9)5) allowed us to presume the 6) 6) hydramacrophyllols A and B from Hydrangeae Dulcis structure of 1 to be the b-D-apiofuranoside of 9. The position Folium, the processed leaves of Hydrangea macrophylla of the apioside linkage was characterized by a nuclear Over- SERINGE var. thunbergii MAKINO (Saxifragaceae). We have hauser effect (NOE) spectroscopy (NOESY) experiment on found two secoiridoid glucoside complexes, hydramacrosides 1, which showed NOE correlations between the anomeric 7) 7) 1) A and B, and four dihydroisocoumarin glycosides, 3R- proton (1--H) of the b-D-apiofuranosyl moiety and the 60- and 3S-phyllodulcin 39-O-glucosides, 3R- and 3S- thun- protons of the b-D-glucopyranosyl moiety. Furthermore, a berginol H 8-O-glucosides, from the dried leaves of this glycosidation shift was observed around the 60-carbon in the plant. Furthermore, phyllodulcin from the dried leaves was 13C-NMR data of 1. The absolute configuration at the 3-posi- found to be ca. 5 : 1 enantiomer mixture at the 3-position.1) tion in 1 was identified by the circular dichroism (CD) spec- As a continuation of this study, we have isolated six new di- trum, which showed the characteristic CD curve for 3R-dihy- 8) 1 2 2 hydroisocoumarin glycosides called 3R- and 3S-hydrangenol droisocoumarin ([q]257 2200, [q]226 3000, [q]221 5800). 49-O-apiosylglucosides (1, 2), 3R- and 3S-thunberginol I 49- Acid hydrolysis of 1 with 5% aqueous sulfuric acid–dioxane O-glucosides (3, 4), thunberginol I 8-O-glucosides (5), and (1 : 1) liberated D-apiose and D-glucose, which were identi- 3S-phyllodulcin 8-O-glucoside (6). This paper deals with the fied by GLC analysis of the trimethylsilyl thiazolide deriva- structure elucidation of these six new dihydroisocoumarin tives.9) Finally, partial methanolysis of 1 with 3% hydrogen glycosides (1—6) and the isomerization reaction at the 3-po- chloride in dry methanol furnished 3R-hydrangenol 49-O- sitions of phyllodulcin and its glycosides. glucosides (9).5) On the basis of this evidence, the structure 3R- and 3S- Hydrangenol 49-O-Apiosylglucosides 3R- of 1 was determined to be 3R-hydrangenol 49-O-b-D-apiofu- hydrangenol 49-O-apiosylglucoside (1) was isolated as a ranosyl (1→6)-b-D-glucopyranoside. 25 2 white powder of negative optical rotation ([a]D 23.9°). 3S-Hydrangenol 49-O-apiosylglucoside (2) was also iso- 25 The IR spectrum of 1 showed absorption bands ascribable to lated as a white powder of negative optical rotation ([a]D hydroxyl, chelated d-lactone, and aromatic ring at 3570, 288.6°). The molecular formula C H O , which was the 2 26 30 13 1670, and 1618 cm 1, while absorption maxima (log e) were same as that of 1, was confirmed from the quasimolecular observed at 245 (3.2) and 314 (2.9) nm. In the positive-ion ion peak at m/z 573 (M1Na)1 in the positive-ion FAB-MS FAB-MS of 1, a quasimolecular ion peak was observed at and by high-resolution MS measurement. The UV and IR 1 1 m/z 573 (M Na) and the molecular formula C26H30O13 of 1 spectra of 2 were found to be very similar to those of 1. was confirmed by high-resolution MS measurement of the Comparison of the 1H- and 13C-NMR (Table 1) for 2 with 1 13 quasimolecular ion peak. The H-NMR (DMSO-d6) and C- those for 1 led us to presume the structure of 2 as the 3- NMR (Table 1) spectra of 1 showed signals assignable to a epimer of 1. The CD spectrum of 2 showed the characteristic 5 8) 2 1 hydrangenol moiety [d 5.73 (dd, J 3.1, 12.1 Hz, 3-H), 6.87 pattern of the 3S-configuration ([q]258 4800, [q]239 3200, 5 5 5 2 (d, J 6.9 Hz, 5-H), 6.90 (d, J 8.1 Hz, 7-H), 7.53 (dd, J 6.9, [q]226 1700). Acid hydrolysis of 2 liberated D-glucose and 9) 8.1 Hz, 6-H); d 7.09 (d, J58.6 Hz, 39, 59-H), 7.47 (d, J5 D-apiose, while treatment of 2 with 3% hydrogen chloride ∗ To whom correspondence should be addressed. © 1999 Pharmaceutical Society of Japan 384 Vol. 47, No. 3 Chart 1 Chart 2 March 1999 385 Table 1. 13C-NMR Data of 1, 2, 3, 4 and 5 8) 1 curve for the 3R-dihydroisocoumarin ([q]256 10000, [q]240 25000), the structure of 3R-thunberginol I 49-O-glucoside 12345 was determined to be 3R-(39-O-methoxy-49-O-b-D-glucopy- C-1 169.1 169.1 169.1 169.0 161.2 ranosylphenyl)-8-hydroxydihydroisocoumarin (3). C-3 80.0 80.1 80.2 80.2 78.3 The 1H- and 13C-NMR (Table 1) spectra of 4 were found to C-4 33.4 33.6 33.5 33.6 35.1 be superimposable on those of 3 and the NOESY experiment C-4a 140.4 140.4 140.4 140.4 141.6 on 4 showed the same NOE correlations as those of 3. This C-5 118.3 118.3 118.2 118.1 120.7 C-6 136.3 136.3 136.3 136.2 134.5 evidence revealed that 4 was the epimer of 3 at the 3-posi- C-7 115.5 115.4 115.4 115.5 128.3 tion. The CD spectrum of 4 showed the characteristic CD C-8 160.9 160.9 161.0 161.0 158.4 2 curve for the 3S-dihydroisocoumarin (8) ([q]255 8300, [q]240 C-8a 108.4 108.4 108.3 108.4 114.3 14800) and consequently, the structure of 3S-thunberginol I C-19 131.4 131.5 131.7 131.7 131.3 9 C-29 128.0 128.0 114.9 114.9 111.9 4 -O-glucoside (4) was determined as shown. C-39 116.1 116.1 146.6 146.6 146.4 Thunberginol I and 3S-Phyllodulcin 8-O-Glucosides C-49 157.6 157.5 148.8 148.8 147.7 Thunberginol I 8-O-glucoside (5) was obtained as a white C-59 116.1 116.1 111.0 111.1 117.5 powder and shown to be a 3-epimeric mixture by examina- C-69 128.0 128.0 119.0 119.0 113.9 1 13 9 tion of the H- and C-NMR spectra. Since the 3-position in 3 -OCH3 55.6 55.6 9 5 showed tautomer-like behavior during the separation proce- 4 -OCH3 55.7 Glc-10 100.3 100.2 99.7 99.7 100.6 dure, we could not separate the 3-epimers of 5. The IR spec- 20 73.1 73.1 73.0 73.1 73.2 trum of 5 showed absorption bands ascribable to hydroxyl, 30 76.4 75.6 76.9 76.9 77.2 d-lactone, and benzene ring at 3325, 1713, and 1601 cm21, 0 4 69.9 69.9 69.5 69.5 69.7 while its UV spectrum showed absorption maxima (log e) at 50 75.7 75.8 76.7 76.7 76.6 60 67.7 67.7 60.5 60.5 60.7 226 (4.1) and 287 (3.6) nm, suggestive of the dihydroiso- Api-1- 109.2 109.2 coumarin structure. The molecular formula, C22H24O10, 2- 78.6 78.5 which was the same as that of 3 or 4, was determined from 3- 78.6 78.5 the positive-ion FAB-MS [m/z 471 (M1Na)1] and by high- 4- 75.5 75.5 resolution MS measurement.
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