Department of Chemistry, University of California, Berkeley, Berkeley, California, 94720, United States.
Angew Chem Int Ed Engl. 2024 Oct 7;63(41):e202409139. doi: 10.1002/anie.202409139. Epub 2024 Sep 5.
Reported herein is the first total synthesis of the poly-pseudoindoxyl natural product baphicacanthcusine A. The synthesis leverages the oxidative rearrangement of indoles to pseudoindoxyls to install vicinal pseudoindoxyl heterocycles in a diastereoselective manner. Key steps include an acid-mediated cyclization/indole transposition, two diastereoselective oxidative ring contractions, and a site-selective C-H oxygenation. The synthesis of the oxidation precursors was guided by recognition of an element of hidden symmetry. This work provides a foundation for the chemical synthesis of other poly-pseudoindoxyl alkaloids.
本文报道了多伪吲哚生物碱 baphicacanthcusine A 的首次全合成。该合成利用吲哚的氧化重排生成伪吲哚，以非对映选择性的方式构建毗邻的伪吲哚杂环。关键步骤包括酸介导的环化/吲哚移位、两个非对映选择性的氧化环收缩，以及位点选择性的 C-H 氧化。氧化前体的合成受到隐藏对称性的启发。这项工作为其他多伪吲哚生物碱的化学合成奠定了基础。
