58(P26) 繊毛虫ブレファリスマの接合誘導物質の新規合成とプローブ開発(ポスター発表の部)

概要

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A new synthesis in enantiomerically pure form of blepharismone (1), a gamone of ciliate Blepharisma japonicum was developed. The Stille reaction in the presence of Pd_2Cl_2(CH_3CN)_2 between trimethyltin derivative 2 and acid chloride 3 derived from (S)-malic acid gave 4 which had carbon skeleton of 1. While N-Boc group of 4 was converted to N-formyl group by HCO_2H/Ac_2O, deprotection of methoxy and clorolalide groups was unsuccssful. Then, the Stille reaction was carried out between 7 and 8, affording 9, the protection groups of which could be removed easily. (S)-blepharismone (1) was synthesized from 9 in two steps (1. HF/pyr. 2. HCO_2H/Ac_2O). (R)-Blepharismone was also synthsized using (R)-malic acid in the same way. The optical purity of synthetic compounds were determined with dimethyl compound 11 derived from 10 by ^1H NMR, using chiral shift reagent (+)-Eu(hfc)_3. It was found that racemization of OH group at 2 position did not occured during the reaction. Synthetic (S)-1 was active as the natural blepharismone in the test of mating induction of Blepharisma, while (R)-1 was inactive at up to 500μg/ml. The photoaffinity label compound of 1 was also designed.
天然有機化合物討論会の論文
1997-07-20