Thunberginols A, B, and F, new antiallergic and antimicrobial principles from Hydrangeae Dulcis Folium.

Medicinal Flowers. XXXX.¹⁾ Structures of Dihydroisocoumarin Glycosides and Inhibitory Effects on Aldose Reducatase from the Flowers of <i>Hydrangea macrophylla</i> var. <i>thunbergii</i>

“…On the basis of all this evidence, the chemical structure of 5 was determined to be as shown. 41) On the other hand, the proton and carbon signals of the aglycon part in the 1 H-and 13 C-NMR spectra of 6 were superimposable on those of thunberginol D, 20,22) except for the signals around the 3′-position, while the proton and carbon signals due to the 3-benzene ring including a glucoside moiety were very similar to those of 5. In addition, on the basis of the DQF-COSY and HMBC experiments (Fig.…”

“…The aqueous layer was further extracted with 1-butanol (1-BuOH) to give a 1-BuOH (12.5%) and a H 2 O (11.0%) soluble fraction. The EtOAc-and 1-BuOH-soluble fractions were subjected to normal-phase and reversed-phase silica gel column chromatography and repeated HPLC to give florahydrosides I (1, 0.068%) and II (2, 0.014%), thunberginol (3R)-thunberginol I 4′-O-β-d-glucopyranoside (10, 0.056%), 18) (+)-3-(4-methoxyphenyl)-8-hydroxy-3,4-dihydroisocoumarin (11, hydrangenol monomethyl ether, 0.011%), 19) phyllodulcin (12, 0.19%), 20,21) hydrangenol 8-O-β-d-glucopyranoside (13, 2.87%), 16,18) thunberginol G 3′-O-β-d-glucopyranoside (14, 0.16%), 16,22) hydrangenol (15, 4.79%), 23,24) thunberginol G (16, 0.067%), 5,25) neochlorogenic acid (17, 0.075%), 26,27) 29) chlorogenic acid (20, 0.054%), 30) chlorogenic acid methyl ester (21, 0.049%), 9,31) taxiphyllin (22, 0.076%), 8,32,33) umbelliferone glucoside (23, 0.11%), 34,35) α-morroniside (24, 0.021%), 36) trans-p-coumaric acid (0.013%), 30,37) and shikimic acid (0.36%) 38) (Fig. 1 C-NMR spectra of 1 were superimposable on those of (3R)-thunberginol E [(3R)-3,4-dihydro-6,8-dihydroxy-3-(3-hydroxy-4-methoxyphenyl) isocoumarin], 22) except for the signals around the 8-position, while the proton and carbon signals due to the dihydroisocoumarin part including glycoside moiety were very similar to those of…”

“…16,18) On the basis of the DQF-COSY and HMBC experiments (Fig. 1), the structure of 4 was determined to be thunberginol C 17,20,22) with glucoside. Next, the position of the glucoside linkage in 4 was confirmed based on HMBC and NOESY experiments, which was showed longrange correlations between H-1″ and C-8 and NOE correlations between H-7 and H-1″, respectively.…”

Suppression byHydrangeae Dulcis FoliumofD-Galactosamine-induced Liver Injuryin Vitroandin Vivo

“…var. thunbergii MAKINO, is a saxifragaceous plant with anticoccidial, 1) antifungal, 2) anti-ulceric, 3) antiallergic, 4) anti-hypercholesterolemic, 3) anti-oxidative, 5) and cholagogic activities.…”

A new total synthesis of natural isocoumarin, thunberginol B

“…thunbergii MAKINO, as antiallergic constituents. [16][17][18][19] Thunberginol B (10) inhibited the histamine release from rat peritoneal mast cells induced by compound 48/80, calcium ionophore A23187, with IC 50 values of less than 100 µM. Structure-activity studies have shown that isocoumarins such as thunberginol A and B are more potent as histamine release inhibitors as compared to the dihydroisocoumarins such as hydrangenol, thunberginol D and E. [18][19][20] In addition, these thunberginols showed antimicrobial activity against oral bacteria.…”