美国加州大学Neil K. Garg团队报道了通过一个应变环状二烯烃立体定向捕获的lissodendoric acid A的全合成。相关研究成果于2023年1月20日发表在国际顶尖学术期刊《科学》。

含有二烯烃的小环是自20世纪60年代以来已知的非常规瞬时化合物。尽管与苯炔几乎同时被发现并提供了许多合成上有利的特征，但应变环状二烯烃在化学合成中的应用相对较少。

研究人员报道了manzamine生物碱lissodenic acid A的简明全合成，这取决于一种短暂的环状二烯烃中间体的区域选择性、非对映选择性和立体特异性捕获的开发。这一关键步骤可快速组装天然产物的氮杂萘啶框架，实现简洁的合成收尾，并实现12步全合成（最长线性序列；总收率0.8%）。这些研究表明，应变环状二烯烃是化学合成中的多功能构建块。

附：英文原文

Title: Total synthesis of lissodendoric acid A via stereospecific trapping of a strained cyclic allene

Author: Francesca M. Ippoliti, Nathan J. Adamson, Laura G. Wonilowicz, Daniel J. Nasrallah, Evan R. Darzi, Joyann S. Donaldson, Neil K. Garg

Issue&Volume: 2023-01-20

Abstract: Small rings that contain allenes are unconventional transient compounds that have been known since the 1960s. Despite being discovered around the same time as benzyne and offering a number of synthetically advantageous features, strained cyclic allenes have seen relatively little use in chemical synthesis. We report a concise total synthesis of the manzamine alkaloid lissodendoric acid A, which hinges on the development of a regioselective, diastereoselective, and stereospecific trapping of a fleeting cyclic allene intermediate. This key step swiftly assembles the azadecalin framework of the natural product, allows for a succinct synthetic endgame, and enables a 12-step total synthesis (longest linear sequence; 0.8% overall yield). These studies demonstrate that strained cyclic allenes are versatile building blocks in chemical synthesis.

DOI: ade0032

Source: https://www.science.org/doi/10.1126/science.ade0032