著者

福井 祐子 田中 良和 久住 高章 岩下 孝 益田 勝吉 野本 享資

出版者

天然有機化合物討論会実行委員会

雑誌

天然有機化合物討論会講演要旨集

巻号頁・発行日

vol.42, pp.55-60, 2000

被引用文献数

1

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Rose breeders have failed to make blue roses. This has been attributed to the lack of blue pigment in the petals. We revealed that mauve rose such as "M'me.Violet" and "Lavande" contain a small amount of blue pigment other than a red anthocyanin, cyanidin 3,5-diglucoside. The major blue pigment of the rose named Rosacyanin A and the minor red one was named Rosacyanin B. The structures of these pigments were elucidated. A high-resolution mass spectrometry showed that Rosacyanin B had the molecular weight of 419.0409 and molecular formula of C_<22>H_<11>O_9. The NMR data showed that Rosacyanin B had an extremely unique structure whose C-1 position of gallic acid is bound to the C-4 position of cyanidin by C-C bond formation. (Fig.2) Rosacyanin A has λ max 590nm (MeOH) of the ultraviolet and visible absorption spectrum, and a molecular formula of C_<56>H_<37>O_<31> which is calculated from the molecular weight of 1205.1319 obtained from high-resolution mass spectrometry. As a result of the observation of the isotope shift by the DH exchange of the solvent using a coaxial sample tube in ^<13>C NMR, it was found that the 3-position of flavylium of Rosacyanin B is bonded to the hexahydroxydiphenoyl part of Tellimagrandin II which is a kind of ellagitannin with ether linkage. (Fig.4) To our knowledge, this is the first report of the compound whose gallic acid binds to C-4 position of polyhydroxyflavylium. The only similar compound which binds gallic acid to catechin was obtained from Burkea africana and Peltophorum africanum. The dream of blue roses will come true if we can accumulate Rosacyanin A in rose petals.

著者

野本 享資 大船 泰史

出版者

The Society of Synthetic Organic Chemistry, Japan

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.40, no.5, pp.401-414, 1982-05-01 (Released:2009-11-13)

参考文献数

42

被引用文献数

18 23

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Mugineic acid (1), an amino acid isolated from the roots of water-cultured barley (Hordeum vulgare L. var. Minorimugi), is the first phytosiderophore to be shown to play a role in the uptake and transport of iron in higher plants. The structure of 1 was determined as 2 (S), 2' (S), 3' (S), -3'' (S) -N- [3-carboxy-3- (3-carboxy-3-hydroxypropylamino) -2-hydroxypropy1] -2-azetidine-2-carboxylic acid by a direct X-ray crystallographic method, and chemical and physico-chemical studies of the degradated products of 1. Structures of other analogous amino acids from some graminaceous plants were also elucidated.Stereospecific total syntheses of 2'-deoxymugineic acid (9) and avenic acid A (11) were achieved by using common key intermediate 28 obtained from L-α-hydroxy-γ-butyrolactone (17) in short steps. N-Alkylation procedure by means of sodium cyanoborohydride in neutral media were effective for condensation of optically active units (e. g. 16c+24 25).The N, O-protecting groups were removed in two steps at the final stage of the synthesis.The structures and properties of metal complexes of mugineic acid were examined by X-ray crystallographic analysis, the potentiometric titration, spectroscopic, and electrochemical studies.