Tian Junsong, Luo Fan, Zhang Chaoshen, Huang Xin, Zhang Yage, Zhang Lei, Kong Lichun, Hu Xiaochun, Wang Zhi-Xiang, Peng Bo
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004, China.
School of Chemistry and Chemical Engineering, University of the Chinese Academy of Sciences, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2018 Jul 16;57(29):9078-9082. doi: 10.1002/anie.201803455. Epub 2018 Jun 14.
We herein report a robust catalyst-free cross-coupling between ArI(OAc) and α-stannyl nitriles, aided by TMSOTf. The transformation introduces a cyanoalkyl group to the ortho position of ArI(OAc) and simultaneously reduces the aryl iodine(III) to iodide, thus providing α-(2-iodoaryl) nitrile as the product. This transformation could be completed within 5 min at -78 °C and features superb functional-group tolerance and efficient scalability. DFT calculations indicate that the formation of a ketenimine(aryl)iodonium intermediate and subsequent [3,3]-sigmatropic rearrangement are involved as key steps.
我们在此报告了在三氟甲磺酸三甲基硅酯（TMSOTf）辅助下，芳基碘乙酸酯（ArI(OAc)）与α-锡腈之间进行的一种稳健的无催化剂交叉偶联反应。该转化反应将氰基烷基引入到ArI(OAc)的邻位，同时将芳基碘（III）还原为碘化物，从而得到α-(2-碘芳基)腈作为产物。该转化反应在-78 °C下5分钟内即可完成，具有出色的官能团耐受性和高效的可扩展性。密度泛函理论（DFT）计算表明，关键步骤涉及乙烯基亚胺（芳基）碘鎓中间体的形成以及随后的[3,3]-σ迁移重排。
