Isolation and characterisation of (E)-4-hydroxy-2-(hydroxymethyl)but-2-enyl β-d-allopyranoside, the major soluble carbohydrate in leaves of the fern Cardiomanes reniforme

Redgwell, Robert J.; Beever, Ross E.; Bieleski, R. L.; Laracy, E. P.; Been, Michael H.

doi:10.1016/0008-6215(90)84274-x

Cited by 7 publications

(9 citation statements)

References 18 publications

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“…The basic hydrolysis of 9 afforded an allopyranoside, the 1 H-NMR spectrum of which was identical to that of cardiomanol (12) obtained from the fern Cardiomanes reniforme, 13) and also isolated from the present species. Acid hydrolysis of 9 gave a caffeic acid, confirming the presence of the caffeoyl group, and its position was apparent from the downfield shift of the H-3Ј proton (d 6.49) in the 1 H-NMR spectrum of 9.…”

supporting

confidence: 59%

“…The acid hydrolysis of 8-11 gave an allose identified by GC-MS analysis and comparison with its authentic sample, confirming the presence of allose in the molecule of 8-11. The 1 H-NMR spectrum of 9 was similar to that of cardiomanol (12), 2,13) except for the appearance of five signals due to a caffeoyl group at d 6.…”

mentioning

confidence: 68%

“…The n-butanol-soluble fraction was subjected to repeated chromatography on DIAION HP-20, silica gel, and Sephadex LH-20 columns, followed by preparative HPLC to yield thirteen glycosides, hymenosides K-W (1, 3-11, 15-17), together with methyl (3R,5R)-hydroxy-(b-D-glucopyranosyloxy)-hexanoate (19). 2) Hymenoside K (1), [a] D Ϫ18.5°, is a glucoside, as evidenced by the signals attributed to a b-glucopyranose unit in the 1 H-and 13 C-NMR spectra (Tables 1, 2). Actually, the 1 H-NMR of 1 showed an anomeric proton at d 4.88 coupled with H-2Ј at d 5.65 (br t, Jϭ8 Hz).…”

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confidence: 99%

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New Glycosides from the Japanese Fern Hymenophyllum barbatum.

Toyota

Oiso

Asakawa

2002

CHEMICAL & PHARMACEUTICAL BULLETIN

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We have focused on the bioactive constituents and chemosystematics of bryophytes and pteridophytes, as well as the evolutionary relationship between terrestrial sporeforming green plants and algae using their characteristic chemical indicators. [1][2][3][4][5][6][7][8][9] Two different traditional views of the evolutionary relationships between bryophytes and pteridophytes have been reported. 10) If ferns and bryophytes are indeed close to the main line of evolution of other vascular plants, then indicators of such links may be present in some chemical congruence. In our continuing chemosystematic research on cryptogamous plants, including bryophytes and pteridophytes, we reported that an acyclic bisbibenzyl characteristic of liverworts was present in the fern Hymenophyllum barbatum. 4)The compound was considered to be a chemical fossil that could link bryophytes and ferns.In the course of the investigation of bioactive substances of New Zealand pteridophytes and bryophytes, we found that some ferns contain a potent hot-tasting substance. This resulted in the isolation of (Ϫ)-polygodial from the New Zealand fern Blechnum fluviatile.11) Recently, we reported the isolation of hemiterpene glycosides, hymenoside A-J, which had a bitter or weakly hot taste, from the Japanese fern Hymenophyllum barbatum. 1,2)After the extraction of H. barbatum with methanol, the crude extract was partitioned between water and ethyl acetate, and then extracted with n-butanol. The n-butanol-soluble fraction was subjected to repeated chromatography on DIAION HP-20, silica gel, and Sephadex LH-20 columns, followed by preparative HPLC to yield thirteen glycosides, hymenosides K-W (1, 3-11, 15- Thirteen glycosides and methyl (3R,5R)-5-hydroxy-(b b-D-glucopyranosyloxy)-hexanoate were newly isolated from the Japanese fern Hymenophyllum barbatum, although our previous work revealed the isolation of hemiterpene glycosides, hymenosides A-J, from the same species. The structures of the newly isolated glycosides were elucidated by extensive two-dimensional (2D) NMR and/or chemical evidence. The structures of those aglycones were divided into four types, 2-methyl-but-2-ene-1,4-diol, 2-hydroxymethyl-but-2-ene-1,4-diol, 2-methylene-butane-1,3,4-triol, and 3-hydroxy-5-hexanolide. The sugar moieties, which were acylated by phenylacetic acid derivatives, were also established by chemical and spectroscopic methods. Eight glucosides of the isolated compounds in the present investigation had a bitter or weakly pungent taste. It is clear that a phenylacetyl group attached to glucose or allose as an ester is necessary for the bitter taste.

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confidence: 68%

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confidence: 99%

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New Glycosides from the Japanese Fern Hymenophyllum barbatum.

Toyota

Oiso

Asakawa

2002

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…Hydrolysis of 1 in 20% KOH aqueous solution gave a glycoside 2, of which the 1 H-and 13 C-NMR spectral data were identical to those of (E)-4-hydroxy-2-(hydroxymethyl) but-2-enyl b-D-allopyranoside (cardiomanol), which has been isolated from the fern Cardiomanes reniforme (Hymenophyllaceae) 2) and also isolated from the present species. To confirm a sugar moiety of 1, acidic hydrolysis of 1 and 2 was performed with 5% H 2 SO 4 .…”

supporting

confidence: 52%

New Bitter-Tasting Hemiterpene Glycosides from the Japanese Fern Hymenophyllum barbatum.

Toyota

Oiso

Asakawa

2001

CHEMICAL & PHARMACEUTICAL BULLETIN

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Differing traditional views of the evolutionary relationships between bryophytes and pteridophytes have been presented. If the ferns and bryophytes are indeed close to the main line of evolution of other vascular plants, then indicators of such links may be present in some chemical congruence. In our continuing chemosystematic research on cryptogamous plants, including bryophytes and pteridophytes, we reported that an acyclic bisbibenzyl characteristic of liverworts was present in the fern Hymenophyllum barbatum. 1)The compound was considered to be a chemical fossil that could link bryophytes and ferns.After the extraction of H. barbatum with methanol, the crude extract was partitioned between water and ethyl acetate, and then n-butanol. The ethyl acetate-soluble fraction was subjected to repeated chromatography on silica gel and Sephadex LH-20 columns, followed by preparative HPLC to yield four hemiterpene glycosides, hymenosides G-J (1, 4, 7, 9), together with hymenosides A-F (Fig. 1). 1)Hymenoside G (1), [a] D Ϫ26.3°, showed a broad absorption band of a hydroxyl group at 3391 cm Ϫ1 and intense carbonyl absorption at 1732 cm Ϫ1 in the Fourier transform (FT)-IR spectrum. The presence of an aromatic ring was apparent from UV absorption at 284 nm and signals due to aromatic protons at d 6.87-7.45 in the 1 H-nuclear magnetic resonance (NMR) spectrum of 1. There were also signals of four oxygenated methylene groups, three isolated arylic methylene groups, five oxygenated methine protons, an olefinic proton, and three sets of protons on a 1,3,4-trisubstituted aromatic ring, as shown in Table 1 Hydrolysis of 1 in 20% KOH aqueous solution gave a glycoside 2, of which the 1 H-and 13 C-NMR spectral data were identical to those of (E)-4-hydroxy-2-(hydroxymethyl) but-2-enyl b-D-allopyranoside (cardiomanol), which has been isolated from the fern Cardiomanes reniforme (Hymenophyllaceae)2) and also isolated from the present species. To confirm a sugar moiety of 1, acidic hydrolysis of 1 and 2 was performed with 5% H 2 SO 4 . D-(ϩ)-allose was detected as the sugar moiety of 1 by capillary GC-MS of its hexaacetate and HPLC analysis with a chiral detector. Further purification of the resulting mixture of the hydrolysis of 1 gave a 3,4-dihydroxyphenylacetic acid, of which the spectral data were identical to those of the authentic sample. The 1 H-NMR spectrum of 2 showed an anomeric proton at d 5.40 (1H, d, Jϭ8 Hz, H-1Ј), although it was observed at d 5.39 as broad singlet in the 1 H-NMR spectrum of 1. The broad singlet signal was correlated to two methine carbon signals at d 98.0 (C-1Ј) and 70.8 (C-2Ј) in the heteronuclear multiple quantum coherence (HMQC) spectrum of 1.It is interesting to note that the chemical shifts of anomeric and H-2Ј protons of 1 had an equivalent in its 1 H-NMR spectrum. Acetylation of 1 gave the nonaacetate 3, of which the anomeric proton signal was observed at d 5.19 (d, Jϭ8 Hz) in its 1 H-NMR spectrum. The configuration of the anomeric position of 1 was determined to be b on the basis of the coupling ...

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“…The sugar fraction was studied by standard methods in use in the laboratory for quantifying and identifying normal and unusual sugars and polyols: TLC, GLC, capillary GC, and mass spectrometry (Redgwell 1980;Redgwell et al 1990;Bieleski et al 1992). Most separations were carried out by GLC of trisilyl derivatives using OV101 silicone in a stainless steel column (Redgwell et al 1990).…”

Section: Separation Of Sugarsmentioning

confidence: 99%