Ｈｅｔｉｓａｎ型トリカブトアルカロイドの合成研究―（±）‐Ｎｏｍｉｎｉｎｅの全合成―

• 村竹 英昭

  財団法人乙卯研究所

書誌事項

タイトル別名

• Synthetic Studies of Hetisan-type Aconite Alkaloids-Total Synthesis of (.+-.)-Nominine-
• Hetisanガタ トリカブトアルカロイド ノ ゴウセイ ケンキュウ Nominine ノ ゼンゴウセイ
• Total Synthesis of (±) -Nominine
• (±) -Nominineの全合成

抄録

A total synthesis of (±) -nominine 1, a heptacyclic hetisan-type aconite alkaloid isolated from Aconitum sanyoense Nakai, was achieved by use of the palladium-catalyzed intramolecular α-arylation of formyl group. The synthesis is composed of forty steps starting from 1-bromo-2- (2-iodoethyl) -4-methoxybenzene 63 in 0.15% overall yield, and constitutes the first total synthesis of a hetisan-type aconite alkaloid, the sole representative aconite skeleton whose total synthesis has remained unsuccessful. The other key steps include (i) acetal ene-reaction to form the C14-C20 bond 55→56, (ii) stereoselective hydrocyanation 57→58, (iii) LiAlH₄ reduction of cyano-enol silyl ether to form the N-C 6 bond 58→59, and (iv) radical cyclization from enyne precursor to construct the methylenebicyclo [2.2.2] octane framework 60→61. Completion of the synthesis was verified unambiguously by single crystal X-ray analysis of the resulting (±) -nominine to confirm its crystal structure as well as its molecular structure.

収録刊行物

• 有機合成化学協会誌

  有機合成化学協会誌 64 (3), 237-250, 2006

  公益社団法人 有機合成化学協会

キーワード

• nominine
• aconite alkaloid
• total synthesis
• palladium catalyst
• α-arylation
• X-ray analysis
• hetisan
• ene-reaction
• hydrocyanation
• radical cyclization

詳細情報

• CRID: 1390282680288806272
• NII論文ID: 10017312047
• NII書誌ID: AN0024521X
• DOI: 10.5059/yukigoseikyokaishi.64.237
• ISSN: 18836526
• ISSN: 00379980
• NDL書誌ID: 7874127
• Web Site: http://id.ndl.go.jp/bib/7874127
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I7874127
• 本文言語コード: ja
• データソース種別:
  • JaLC
  • NDL
  • Crossref
  • CiNii Articles
  • KAKEN
• 抄録ライセンスフラグ: 使用不可