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Updated: Oct 24, 2025

A Direct, Early Stage Guanidinylation Protocol for the Synthesis of Complex Aminoguanidine-containing Natural Products

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クリオナスタチンAとBの非対称的全合成

Wei Ju¹, Xudong Wang¹, Hailong Tian¹

¹CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.

Journal of the American Chemical Society

|August 16, 2021

まとめ

ポリ塩化ステロイドのクリオナスタチンAとBの最初の非対称な合成を達成しましたこの合成は,それらの構造的割り当てを修正し,それらをC14エピマーとして明らかにした.

科学分野:

有機化学
総合成
自然製品化学

背景:

クリオナスタチンAとBのような多塩化ステロイドは,潜在的な生物学的活動を持つ複雑な天然製品です.
このような分子の総合成は,複雑な構造と複数のステレオセンターのために重要な課題を提示します.

研究の目的:

クリオナスタチンAとBの最初の完全合成を報告する.
収束し,根本的な断片結合アプローチを利用した非対称な合成経路を確立する.
クリオナスタチンAとBの最終的な構造を明らかにする.

主な方法:

根断片結合を用いたコンバージェント合成
アイルランド - ステレオセンターの導入と移転のための再配置
断片結合のための地域選択性アシル基結合添加.
四次性ステレオセンター形成のための内分子ヘック反応.
準赤道型二塩化装置のためのダイアステロセレクティブオレフィン二塩化.

主要な成果:

クリオナスタチンAとBの非対称的全合成が成功しました.
ステレオ化学リレーを介してキーステレオセンターの導入と転送.
分子内ヘック反応を用いたC10四次性ステレオセンターの形成.
ディアステレオ選択的二塩化による擬赤道二塩化物の形成.
提案された構造を修正し,クリオナスタチンAとBをC14エピマーとして識別する.

結論:

開発された合成戦略は,多塩化ステロイドへの強力な経路を提供します.
合成により,クリオナスタチンAとBのC14エピマーとしての構造的分類が確認された.
この研究は,複雑な塩素化天然製品の合成方法論を進めている.

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