96
Vol. 62, No. 1
Industry Press, Beijing, 2002, pp. 751–755.
2) Son K. H., Jung K. Y., Chang H. W., Kim H. P., Kang S. S., Phyto-
chemistry, 35, 1005–1008 (1994).
3) Kwak W. J., Han C. K., Chang H. W., Kim H. P., Kang S. S., Son K.
H., Chem. Pharm. Bull., 51, 333–335 (2003).
H-12), 4.26 (1H, d, J=10.4Hz, H-23a), 3.62 (1H, d, J=10.4Hz,
H-23b), 1.19 (3H, s, Me-27), 1.11 (3H, s, Me-26), 1.01 (3H, s,
Me-25), 0.91 (3H, s, Me-30), 0.90 (3H, s, Me-24), 0.85 (3H, s,
1
Me-29); H-NMR signals for the sugar moieties: see Table 1;
13C-NMR (C5D5N) δ: 38.9, 26.1, 82.0, 43.4, 47.7, 18.2, 32.3,
40.0, 48.2, 36.9, 23.9, 122.7, 144.1, 42.2, 28.6, 23.4, 47.1,
41.9, 46.3, 30.7, 34.0, 32.9, 64.5, 13.6, 16.2, 17.5, 25.9, 176.6,
33.1, and 23.8 (C-1–C-30), 106.6, 73.1, 74.7, 69.6, and 66.9
(C-1′–C-5′), 94.8, 75.5, 79.6, 70.9, 77.4, and 69.2 (C-1″–C-6″),
101.5, 72.2, 72.5, 73.8, 69.8, and 18.8 (C-1‴–C-6‴), 105.5, 72.4,
78.7, 69.0, and 66.7 (C-1⁗–C-5⁗), 21.2 and 170.6 (acetyl).
Alkaline Hydrolysis of 4 Compound 4 (5.0mg) was al-
kaline hydrolyzed as described for 2 and 3 to give 6 (2.8mg).
Loniceroside J (5): Amorphous solid. [α]D23 -15.7 (c=0.10,
MeOH). HR-ESI-TOF-MS m/z: 1227.6122 [M+Na]+ (Calcd for
C59H96NaO25: 1227.6137). IR νmax (film) cm−1: 3359 (OH), 2927
4) Shoji Y., Kobayashi N., Nohara T., Shoyakugaku Zasshi, 44, 339–
342 (1990).
5) Kawai H., Kuroyanagi M., Umehara K., Ueno A., Satake M., Chem.
Pharm. Bull., 36, 4769–4775 (1988).
6) Machida K., Sasaki H., Iijima T., Kikuchi M., Chem. Pharm. Bull.,
50, 1041–1044 (2002).
7) Jitsuno M., Mimaki Y., Phytochemistry, 71, 2157–2167 (2010).
8) Yokosuka A., Sato K., Yamori T., Mimaki Y., J. Nat. Prod., 73,
1102–1106 (2010).
9) Matsuo Y., Watanabe K., Mimaki Y., J. Nat. Prod., 72, 1155–1160
(2009).
10) Mimaki Y., Doi S., Nat. Prod. Commun., 3, 903–910 (2008).
11) Mimaki Y., Doi S., Kuroda M., Yokosuka A., Chem. Pharm. Bull.,
55, 1319–1324 (2007).
1
(CH), 1736 (C=O); H-NMR (C5D5N) δH: 5.41 (1H, brs, H-12),
1.24 (3H, s, Me-27), 1.19 (3H, s, Me-23), 1.14 (3H, s, Me-24),
12) Kuroda M., Aoshima T., Haraguchi M., Young M. C. M., Sakagami
H., Mimaki Y., J. Nat. Prod., 69, 1606–1610 (2006).
1.05 (3H, s, Me-26), 0.91 (3H, s, Me-30), 0.87 (3H×2, each s,
1
Me-25 and Me-29); H-NMR signals for the sugar moieties: 13) Mimaki Y., Harada H., Sakuma C., Haraguchi M., Yui S., Kudo T.,
see Table 1; 13C-NMR (C5D5N) δ: 39.0, 26.8, 88.9, 39.4, 56.1,
Yamazaki M., Sashida Y., Helv. Chim. Acta, 87, 851–865 (2004).
14) Mimaki Y., Kuroda M., Yokosuka A., Harada H., Fukushima M.,
Sashida Y., Chem. Pharm. Bull., 51, 960–965 (2003).
15) Mimaki Y., Harada H., Sakuma C., Haraguchi M., Yui S., Kudo T.,
Yamazaki M., Sashida Y., Bioorg. Med. Chem. Lett., 13, 623–627
(2003).
16) Watanabe K., Mimaki Y., Sakagami H., Sashida Y., Chem. Pharm.
18.6, 32.3, 79.9, 48.0, 36.9, 23.7, 122.7, 144.1, 42.2, 28.7, 23.3,
47.2, 41.9, 46.4, 30.7, 34.0, 33.1, 28.1, 17.1, 15.7, 17.4, 25.9,
176.6, 33.1, and 23.8 (C-1–C-30), 105.4, 77.8, 79.9, 72.1, 78.1,
and 62.8 (C-1′–C-6′), 101.7, 72.4, 72.5, 74.1, 69.6, and 18.7
(C-1″–C-6″), 94.7, 75.3, 79.6, 71.1, 77.6, and 69.0 (C-1‴–C-6‴),
101.4, 72.2, 72.5, 73.8, 69.7, and 18.7 (C-1⁗–C-6⁗), 105.5,
74.8, 78.0, 71.0, and 67.0 (C-1″‴–C-5″‴).
Bull., 50, 121–125 (2002).
17) Mimaki Y., Fukushima M., Yokosuka A., Sashida Y., Natural Medi-
Acid Hydrolysis of 5 A solution of 5 (5.0mg) was sub-
jected to acidic hydrolysis as described for 1 to yield an agly-
cone fraction (1.1mg) and a sugar fraction (2.1mg). The agly-
cone fraction was chromatographed on silica gel eluted with
CHCl3–MeOH (19:1) to give olaenolic acid (0.2mg). HPLC
analysis of the sugar fraction under the same conditions as in
the case of 1 showed the presence of L-rhamnose, D-xylose,
and D-glucose; tR (min) 8.48 (L-rhamnose, negative optical
rotation), 10.84 (D-xylose, positive optical rotation), 18.59 (D-
glucose, positive optical rotation).
cines, 55, 217 (2001).
18) Kuroda M., Mimaki Y., Harada H., Sakagami H., Sashida Y., Natu-
ral Medicines, 55, 134–138 (2001).
19) Kuroda M., Mimaki Y., Sashida Y., Kitahara M., Yamazaki M., Yui
S., Bioorg. Med. Chem. Lett., 11, 371–374 (2001).
20) Yui S., Ubukata K., Hodono K., Kitahara M., Mimaki Y., Kuroda
M., Sashida Y., Yamazaki M., Int. Immunopharmacol., 1, 1989–
2000 (2001).
21) Mimaki Y., Kuroda M., Asano T., Sashida Y., J. Nat. Prod., 62,
1279–1283 (1999).
22) Lin L.-M., Zhang X.-G., Zhu J.-J., Gao H.-M., Wang Z.-M., Wang
W.-H., J. Asian Nat. Prod. Res., 10, 925–929 (2008).
23) Kizu H., Shimana H., Tomimori T., Chem. Pharm. Bull., 43, 2187–
2194 (1995).
References
1) Xiao P. G., Li D. P., Yang S. L., “Modern Chinese Materia Medica,”
1st ed., Vol. III, ed. by Xiao P. G., Li D. P., Yang, S. L., Chemical
24) Agrawal P. K., Phytochemistry, 31, 3307–3330 (1992).