Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing 100084, China.
J Org Chem. 2021 Apr 16;86(8):5727-5743. doi: 10.1021/acs.joc.1c00209. Epub 2021 Mar 31.
The palladium-catalyzed intramolecular dearomative Heck reaction of 2,3-disubstituted indoles serves as an access to spiro-indoline products. Herein, we report an efficient construction of indoline/indolenine core stuctures via a dearomative Heck reaction of simple 2,3-disubstituted indoles with all-carbon tethers and the subsequent aza-semipinacol rearrangement. The Heck reaction features a high C2-selectivity, and the stereospecific aryl/alkyl migration selectivity has been investigated by DFT calculations. Using this method, we accomplished the formal total synthesis of alkaloids vincorine.
钯催化的 2,3-二取代吲哚的分子内去芳构化 Heck 反应可作为获得螺吲哚啉产物的途径。在此，我们报告了一种通过简单的 2,3-二取代吲哚与全碳连接基团的去芳构化 Heck 反应以及随后的氮杂半频哪醇重排来高效构建吲哚啉/吲哚啉核心结构的方法。该 Heck 反应具有高 C2 选择性，并且通过 DFT 计算研究了立体特异性芳基/烷基迁移选择性。使用该方法，我们完成了生物碱长春碱的正式全合成。
