Lindner Henry, Amberg Willi M, Martini Tristano, Fischer David M, Moore Eléonore, Carreira Erick M
Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
Angew Chem Int Ed Engl. 2024 May 6;63(19):e202319515. doi: 10.1002/anie.202319515. Epub 2024 Mar 22.
We report a general, intramolecular cycloisomerization of unactivated olefins with pendant nucleophiles. The reaction proceeds under mild conditions and tolerates ethers, esters, protected amines, acetals, pyrazoles, carbamates, and arenes. It is amenable to N-, O-, as well as C-nucleophiles, yielding a number of different heterocycles including, but not limited to, pyrrolidines, piperidines, oxazolidinones, and lactones. Use of both a benzothiazinoquinoxaline as organophotocatalyst and a Co-salen catalyst obviates the need for stoichiometric oxidant or reductant. We showcase the utility of the protocol in late-stage drug diversification and synthesis of several small natural products.
我们报道了一种未活化烯烃与亲核试剂的分子内环异构化反应。该反应在温和条件下进行，能耐受醚、酯、保护胺、缩醛、吡唑、氨基甲酸酯和芳烃。它适用于N -、O -以及C -亲核试剂，可生成多种不同的杂环化合物，包括但不限于吡咯烷、哌啶、恶唑烷酮和内酯。使用苯并噻嗪并喹喔啉作为有机光催化剂和钴 - 萨伦催化剂，无需化学计量的氧化剂或还原剂。我们展示了该方法在后期药物多样化和几种小分子天然产物合成中的实用性。
