本研究は、アミド基を1,3-双極子等価体として利用する合成法の開発に取り組んだ。まず初めに、N-ヒドロキシアミドに対しIr触媒を用いた還元的ニトロン合成と、有機リチウム試薬を用いた求核的ニトロン合成法を開発した。次に、開発した反応を含窒素天然物へ応用し、シリンドリシンCの全合成を達成した。Ir触媒による手法は、アゾメチンイリド合成への展開が可能であり、アスピドスペルミジンの全合成を達成した。
1,3-Dipoles have been widely used as promising intermediates for the synthesis of complex heterocyclic compounds found in biologically active natural products and pharmaceuticals. Therefore, the development of practical methods to generate highly functionalized 1,3-dipoles is an important research topic in the modern organic synthesis. Our research group has proposed that easily available amides can serve as synthetic equivalents of 1,3-dipoles through reduction or nucleophilic addition. In this project, we developed Ir-catalyzed reduction or nucleophilic addition to N-hydroxyamides. The method provided functionalized nitrones, and was successfully applicable to the total synthesis of cylindricine C. The iridium-catalyzed reduction was also applied to the synthesis of functionalized azomethine ylides, which resulted in the total synthesis of aspidospermidine.

研究種目 : 基盤研究 (C) (一般)
研究期間 : 2018～2020
課題番号 : 18K05127
研究分野 : 有機化学