通过炔烃官能化实现血根碱B五环核心的合成。

Farhi Jonathan, Rezgui Samir P, Yu Hao, Stoltz Brian M

The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.

Org Lett. 2025 May 30;27(21):5390-5393. doi: 10.1021/acs.orglett.5c01332. Epub 2025 May 15.

Sanguinones A and B are recently isolated pyrroloiminoquinone alkaloids possessing a rare C4 carboxylic acid. We report a synthetic approach toward the full carbon and nitrogen pentacyclic core of sanguinone B, with the correct oxidation at C4. Highlights of this approach include the application of a Larock/Buchwald-Hartwig annulation cascade to access a key tricyclic intermediate and alkyne functionalization using Rh(I) or Cu(I) catalysis to access hindered benzylic ketones.

血根碱A和B是最近分离出的含有罕见C4羧酸的吡咯并亚氨基醌生物碱。我们报道了一种合成血根碱B完整碳氮五环核心的方法，该方法在C4处具有正确的氧化态。该方法的亮点包括应用Larock/Buchwald-Hartwig环化级联反应来获得关键的三环中间体，以及使用Rh(I)或Cu(I)催化进行炔烃官能化以获得受阻的苄基酮。