open access

https://doi.org/10.11501/3097885

https://hdl.handle.net/2115/51267

オオワライタケの毒成分ジムノピリン類の立体化学に関する研究

英語

1994-09-30

Hokkaido University

126p.

Gymnopilins (1) were isolated as bitter principles from the poisonous mushroom Gymnopilus spectabilis, which was called Ohwaraitake (big laughter mushroom) in Japan, by Matsumoto and Nozoe's groups about 10 years ago. Neuroexcitatory activity as well as cytotoxicity of 1 has been recently disclosed and focused in the fields of pharmacology and physiology. Gymnopilins (1) are isoprenoid esters and hydrolyzed to oligoisoprenoid polyols named gymnoprenols (2) and 3-hydroxy-3-methylglutaric acid (HMGA). It naturally occurs as a mixture of many analogous compounds which are different each other in the number of isoprene and 2-isoprenol units. The gross structures of 1 were previously determined as shown in Fig 1 and the absolute configurations of the 1,2,3-triol part and the HMGA moiety were recently established as (2R,3S) and (3S) configurations, respectively, but the stereochemistry of the sequential 1,5-diol part remained still unknown. This thesis is mainly concerned with the presumption of the unclear stereochemistries of the 1,5-oligodiol moieties of gymnopilins (1) and gymnoprenols (2). lt should be emphasized that discrimination among diastereoisomeric gymnoprenols (2) was deduced to be very difficult since all synthetic diastereoisomers with respect to the sequential 1,5-diol parts showed the same NMR spectra and the same retention times in HPLC. A new method to amplify the stereochemical difference among gymnoprenol analogues had to be developed for this research. ln this thesis, the author would like to describe extraction and purification of gymnoprenols, synthesis of some gymnoprenol analogues having various diastereoisomeric 1,5-polyol structures, and finally presumption of the stereochemistry of the natural products in comparison with these synthetic compounds by means of the newly developed method.

1994-09-30

甲第3482号

博士(理学)

博士論文

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