98(P-55) インジウム(0)を用いた立体選択的アリル化反応とManzacidin A合成研究への応用(ポスター発表の部)

• 海江田 啓

  京大院薬

• 柳田 玲子

  京大院薬

• 竹本 佳司

  京大院薬

書誌事項

タイトル別名

• 98(P-55) Indium(0)-mediated diastereoselective allylation reaction and its application to synthesis of Manzacidin A

抄録

Indium is comparatively stable in air. The first ionization potential of indium (5.8 eV) is as low as that of Na (5.1eV). For these reasons, indium is one of the most notable metals at present. Two allylation methods (Barbier-type allylation and palladium mediated allylation) of optically active iminoalcohol-type aldimine with indium were developed. The reaction proceeded regio- and diastereoselectively to give optically active homoallylamine derivatives 5 in high yields. Manzacidins are bromopyrrole alkaloids and are found to be pharmacologically useful as α-adrenoceptor blockers, antagonists of serotonergic receptor, and actomyosin ATPase activators. We planned the synthesis of manzacidin A via stereoselective methallylation of oxazolidines 3 with indium. The methallylated compound 8 was obtained in good yield. Then we planed a novel ring closing method which was applied to the optically active homoallylated compoun 10 and allylated compoun 12. These reactions proceeded smoothly via 6-Exo-Trig and 5-Exo-Trig cyclization to give halogenated compounds 11 and 13, respectively. We next examined the conversion of the compound 8 into the guanidine 16. Construction of the tetrahydropyrimidin ring was performed by the novel intramolecular cyclization of guanidine compound 15 with NBS to give the bicyclic compound 16 in good regio- and stereoselectivities. Further synthetic studies of Manzacidin A is now in progress.

収録刊行物

• 天然有機化合物討論会講演要旨集

  天然有機化合物討論会講演要旨集 43 (0), 581-586, 2001

  天然有機化合物討論会実行委員会

詳細情報

• CRID: 1390001206079259264
• NII論文ID: 110006682143
• DOI: 10.24496/tennenyuki.43.0_581
• ISSN: 24331856
• 本文言語コード: ja
• データソース種別:
  • JaLC
  • CiNii Articles
• 抄録ライセンスフラグ: 使用不可