Diarylheptanoid Glycosides Research Articles

Hirsunin, an ellagitannin with a diarylheptanoid moiety, from Alnus hirsuta var. Microphylla

A novel ellagitannin, hirsunin, was isolated from the leaves of Alnus hirsuta var. microphylla and the structure which consists of diarylheptanoid glycoside (oregonin) and ellagitannin (praecoxin A) moieties connected through an ester linkage has been elucidated. Furthermore, the occurrence of the seven known hydrolysable tannins, pedunculagin, praecoxin A, 1,2,6- and 1,4,6-tri- O-galloyl-β- d-glucoses, 1-desgalloyleugeniin, 1-desgalloylrugosin F, and rugosin F, along with oregonin and gentisic acid 5- O-β- d-(6′- O-galloyl)-glucopyranoside has also been demonstrated.

Two myricanol glycosides from Myrica rubra and revision of the structure of isomyricanone

Two new diarylheptanoid glycosides were isolated from the stem bark of Myrica rubra ( Myricaceae). On the basis of spectral and chemical evidence, their structures were established as myricanol 5- O-β- d-glucopyranosyl-(1→3)-β- d-glucopyranoside and myricanol 5- O-α- l-arabinofuranosyl-(1→6)-β- d-glucopyranoside, respectively. The structure of isomyricanone was also reexamined chemically and physicochemically, and a revised structure is presented.

Studies on the constituents of aceraceae plants. VII. Diarylheptanoids from Acer griseum and Acer triflorum.

A diarylheptanoid glycoside, named aceroside IX (1), C30H40O12, [α]D -63.5°, was isolated from the stem bark of Acer griseum and A. triflorum. Another diarylheptanoid glycoside, named aceroside X (2), C25H31O8, mp 121°, [α]21D -29.7°, and catechin were isolated from the stem bark of A. griseum and detected by thin layer chromatography in the case of A. triflorum. On acid hydrolysis 1 yielded a new diarylheptanoid, acerogenin G (3), C19H22O3, which was identified as a ketonic derivative of (-)-centrolobol (5), and sugars, glucose and apiose. On partial hydrolysis, 1 gave aceroside X (2) and apiose. The sugar moiety of aceroside IX is bound to the phenolic hydroxyl at C-4 of acerogenin G (3) from the results of mass spectral analysis of 3 and its monomethyl ether (6), the latter of which was formed on methylation of 1 followed by acid hydrolysis. Acerosides (1) and X (2) were determined to be the 4-O-β-D-apiofuranosyl-(1→6)-β-D-glucopyranoside and the 4-O-β-D-glucopyranoside of acerogenin G, respectively, on the basis of carbon-13 nuclear magnetic resonancence spectral analyses in comparison with the spectrum of aceroside VIII (7).

Constituents of Myrica rubra. III. Structures of two glycosides of myricanol.

Two new diarylheptanoid glycosides (1 and 2) were isolated together with vanillic acid and six known triterpenoids, maslinic acid, alphitolic acid, arjunolic acid, myricolal, oleanolic acid and oleanolic acid acetate, from the stem bark of Myrica rubra SIEB. et ZUCC. (Myricaceae). On the basis of spectral and chemical evidence, the structures of 1 and 2 were established as myricanol 5-O-β-D-(6'-O-galloyo)-glucopyranoside and myricanol 5-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside, respectively.

Studies on the constituents of aceraceae plants. VI. Revised stereochemistry of (-)-centrolobol, and new glycosides from Acer nikoense.

Two diarylheptanoid glycosides, named aceroside VII (8), C25H34O8, mp 144-145°C, [α]15D -28.4°, and aceroside VIII (9), C30H42O12, [α]15D -64.8° were isolated from the stem bark of Acernikoense MAXIM. (Aceraceae). On acid hydrolysis 8 yielded (-)-centrolobol (10) and glucose, while 9, on partial hydrolysis, gave 8 and apiose. Acerosides VII (8) and VIII (9) were determined to be the 3-O-β-D-glucopyranoside and the 3-O-β-D-apiofuranosyl-(1→6)-β-D-glucopyranoside of (-)-centrolobol (10), respectively, on the basis of carbon-13 nuclear magnetic resonance (13C-NMR) spectral analyses and additional chemical data.The absolute configuration S for (-)-centrolobol (10) has been claimed, but the authors propose its revision to R(-) on the basis of Brewster's empirical rule on the correlation between absolute configuration and optical rotation. The stereochemistries of some compounds related to 10 such as acerogenin A (1) and (-)-centrolobin should also be revised. At the same time, partial revision of the 13C-NMR signal assignments for acerosides III (3) and VI (4) is also necessary.

The structures of four diarylheptanoid glycosides from the female flowers of Alnus serrulatoides

Four diarylheptanoid monoglycosides (2a), (2b), (3), and (4), in addition to the hydroxy ketone (1), were isolated from the female flowers of Alnus serrulatoides. On the basis of the physicochemical and the X-ray crystallographic analyses, these were characterized as (5S)-1,7-bis(3,4-dihydroxyphenyl)-5-hydroxyheptan-3-one (1), (5S)-1-(4-hydroxyphenyl)-7-(3,4-dihydroxyphenyl)-5-(β-D-xylo-pyranosyloxy)heptan-3-one (2a), (5S)-1-(3,4-dihydroxyphenyl)-7-(4-hydroxyphenyl)-5-(β-D-xylo-pyranosyloxy)heptan-3-one (2b), (5S)-1,7-bis(3,4-dihydroxyphenyl)-5-(β-D-xylopyranosyloxy)-heptan-3-one (3), and (5S)-1,7-bis(3,4-dihydroxyphenyl)-5-(β-D-glucopyranosyloxy)heptan-3-one (4), respectively. Of these compounds, the glycosides (2a), (2b), and (4) are new.

Diarylheptanoids in the bark of Myrica rubra Sieb. et Zucc

A diarylheptanoid glycoside named myricanol glucoside (3), C27H36O10·1/2 H2O, mp 220-223°C, [α]D-53.7°, was isolated from the stem bark of Myrica rubra in addition to myricanol (1) and myricanone (2). On the basis of chemical and spectral evidence the glucoside (3) was elucidated to be myricanol 5-β-D-glucopyranoside. This is the first example as a glucoside of biphenyl-type diarylheptanoid.

Studies on the constituents of aceraceae plants. V. Two diarylheptanoid glycosides and an arylbutanol apiosylglucoside from Acer nikoense.

From the stem bark of Acer nikoense MAXIM. (Aceraceae), three glycosides were isolated, namely aceroside III (1), C30H40O12, mp 138-141°C, [α]D-98.4°, aceroside VI (2), C25H32O8·1/2H2O, mp 124-125°C, [α]D-69.3°, and apiosylepirhododendrin (3), amorphous film (C21H32O11), [α]D-59.5°. On acid hydrolysis, 1 yielded acerogenin A (4), apiose, glucose, and a partially hydrolyzed product 2, while 3 afforded (+)-rhododendrol (11), apiose, and glucose. Inspection of the carbon-13 nuclear magnetic resonance (13C NMR) and the PRFT-NMR spectra of 1 and 3 disclosed that they are apiosyl-(1→6)-glucosides. The proton nuclear magnetic resonance (1H NMR) spectral data of their permethylates (6 and 12) and the analytical data of methanolysis products of 6 and 12 established the structures of 1, 2 and 3 as acerogenin A 11-O-β-D-apiofuranosyl-(1→6)-β-D-glucopyranoside, acerogenin A 11-O-β-D-glucopyranoside and (+)-rhododendrol 2-O-β-D-apiofuranosyl-(1→6)-β-D-glucopyranoside, respectively.