Selective ortho C-H Cyanoalkylation of (Diacetoxyiodo)arenes through [3,3]-Sigmatropic Rearrangement.
Selective ortho C-H Cyanoalkylation of (Diacetoxyiodo)arenes through [3,3]-Sigmatropic Rearrangement.
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DOI：
10.1002/anie.201803455
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发表时间：
2018-06
影响因子：
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通讯作者：
Junsong Tian;Fan Luo;Chaoshen Zhang;Xin Huang;Yage Zhang;Lei Zhang;Lichun Kong;Xiaochun Hu;Zhi‐Xiang Wang;Bo Peng
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文献类型：
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作者：
Junsong Tian;Fan Luo;Chaoshen Zhang;Xin Huang;Yage Zhang;Lei Zhang;Lichun Kong;Xiaochun Hu;Zhi‐Xiang Wang;Bo Peng
我们在此报告了一个强大的无催化剂的交叉偶联ArI（OAc）2和α-甲锡腈，辅助TMSOTf。该转化将氰基烷基引入ArI（OAc）2的邻位，同时将芳基碘（III）还原为碘化物，从而得到产物α-（2-碘代芳基）腈。这种转化可以在-78 °C下在5分钟内完成，具有极好的官能团耐受性和高效的可扩展性。DFT计算表明，烯酮亚胺（芳基）碘鎓中间体的形成和随后的[3，3]-σ迁移重排是关键步骤。
We herein report a robust catalyst-free cross-coupling between ArI(OAc)2 and α-stannyl nitriles, aided by TMSOTf. The transformation introduces a cyanoalkyl group to the ortho position of ArI(OAc)2 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.