Ｃｌａｉｓｅｎ転位を鍵反応とする多官能性スピロ化合物の立体選択的構築と天然物合成への応用

• 中崎 敦夫

  東京理科大学薬学部

• 小林 進

  東京理科大学薬学部

書誌事項

タイトル別名

• Stereoselective Synthesis of Highly Functionalized Spirocyclic Compounds based on Claisen Rearrangement and its Application to the Synthesis of Natural Products
• Claisen テンイ オ カギ ハンノウ ト スル タカンノウセイ スピロ カゴウブツ ノ リッタイ センタクテキ コウチク ト テンネンブツ ゴウセイ エノ オウヨウ

抄録

Spirocyclic scaffolds are embedded in many biologically active natural compounds, including candidates for medicines, perfumes and agricultural chemicals. Therefore, a development of efficient synthetic methods directed at those structures is strongly demanded. To this end, we have recently developed synthetic methodologies for two different spirocyclic frameworks, spiro[4.5]decanes and spirocyclic oxindoles, based on Claisen rearrangement. We have developed the Claisen rearrangement protocol by which bicyclic 2-(alkenyl) dihydropy-rans with functionality at C 4 can be transformed to spiro[4.5]decanes in good-to-excellent yields with excellent stereoselectivities. We applied this method to a concise total synthesis of several biologically active spirocyclic sesquiterpenes. Related Claisen rearrangement in (alkenyl)pyranoindole systems can be also achieved. Thus, a one-pot intramolecular Ullmann coupling/Claisen rearrangement sequence from 2-iodoindoles was found to provide spirocyclic oxindoles in good yields with excellent stereoselectivities. We applied this sequence to the synthesis of pyrrolidinoindoline alkaloids.

収録刊行物

• 有機合成化学協会誌

  有機合成化学協会誌 66 (2), 124-138, 2008

  公益社団法人 有機合成化学協会

キーワード

• spirocyclic compounds
• Claisen rearrangement
• total synthesis
• one-pot reaction
• Ullmann coupling

詳細情報

• CRID: 1390001205312836736
• NII論文ID: 10021173601
• NII書誌ID: AN0024521X
• DOI: 10.5059/yukigoseikyokaishi.66.124
• ISSN: 18836526
• ISSN: 00379980
• NDL書誌ID: 9378882
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I9378882
• 本文言語コード: ja
• データソース種別:
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• 抄録ライセンスフラグ: 使用不可