Absolute Stereostructures of 3S-Phyllodulcin, 3R- and 3S-Phyllodulcin Glycosides, and 3R- and 3S-Thunberginol H Glycosides from the Leaves of Hydrangea macrophylla SERINGE var. thunbergii MAKINO

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>

“…(Table 1) spectra of 5, 39) showed signals assignable to a dihydroisocoumarin moiety {ca. 11 : 9 mixture of two diastereoisomers C-NMR spectra of 5 were superimposable on those of thunberginol G 3′-O-β-d-glucopyranoside (14), 16,22) except for the signals around the 4-position. The structure of dihydroisocoumarin moiety including the two hydroxy groups on 5 was confirmed based on DQF and HMBC experiments, which was showed long-range correlations between the following protons and carbons: H-3 and C-4; H-4 and C-3, 5; H-5 and C-8a; H-6 and C-8; H-7 and C-8a.…”

“…The proton and carbon signals of the dihydroisocoumarin part in the 1 Hand 13 C-NMR spectra of 4 were superimposable on those of 1, while the proton and carbon signals due to the 3-phenyl part were very similar to those of hydrangenol 8-O-β-dglucopyranoside (13). 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.…”

“…C-NMR spectra of 3 were superimposable on those of thunberginol G (16), 5,25) 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 7, 16) 8, 16) and 13. 16,18) As shown in Fig. 2, the HMBC experiments revealed long-range correlations between the following protons and carbons: H-4 and C-5, 8a; H-5 and C-4, 8a; H-6 and C-8; H-7 and C-5, 8a; H-2′ and C-3, 4′; H-5′ and C-1′; H-6′ and C-3, 2′, 4′; H-1″ and C-8.…”

“…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…”

Invasion Inhibitors of Human Fibrosarcoma HT 1080 Cells from the Rhizomes of <i>Zingiber cassumunar</i>: Structures of Phenylbutanoids, Cassumunols

“…Previously, we reported the isolation of racemic isocoumarins 29,30) and sesquiterpenes 8,9,31,32) and their formation chemical process from the genuine compounds. Since cassumunols C (3), E (5), F (6), G (7), H (8), and 15 showed no significant optical activity.…”