Shan Yingying, Zhang Xiuhua, Liu Gongle, Li Jianming, Liu Yongwei, Wang Jia, Chen Dianpeng
Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong, China.
Chem Commun (Camb). 2024 Feb 6;60(12):1546-1562. doi: 10.1039/d3cc05880h.
Cyanation has attracted considerable attention in organic synthesis because nitriles are key structural motifs in numerous important dyes, agrochemicals, natural products and drug molecules. As the fourth generation of cyanating reagents, isocyanides occupy a prominent place in the synthesis of nitriles due to their favorable stability, easy operability and high reactivity. In recent years, three types of cyanation with isocyanides have been established: the cleavage of the C-NC bond of tertiary alkyl isocyanides (Type I), the rearrangement of aryl isocyanides with azides (Type II), and the reductive cyanation of ketones with α-acidic isocyanides (Type III). This review focuses on advances in cyanation with isocyanides with an emphasis on reaction scope, limitations and mechanisms, which could reveal their remarkable value and superiority for accessing various nitriles. In addition, the future development prospects of this specific field are also introduced. We believe that this feature article will serve as a comprehensive tool to navigate cyanation with isocyanides across the vast area of synthetic chemistry.
氰化反应在有机合成中备受关注，因为腈是众多重要染料、农用化学品、天然产物和药物分子中的关键结构单元。作为第四代氰化试剂，异腈因其良好的稳定性、易于操作和高反应活性，在腈的合成中占据显著地位。近年来，已建立了三种类型的异腈氰化反应：叔烷基异腈的C-NC键断裂（I型）、芳基异腈与叠氮化物的重排反应（II型）以及酮与α-酸性异腈的还原氰化反应（III型）。本综述重点关注异腈氰化反应的进展，着重于反应范围、局限性和反应机理，这有助于揭示它们在合成各种腈类化合物方面的显著价值和优势。此外，还介绍了这一特定领域的未来发展前景。我们相信，这篇专题文章将成为在广阔的合成化学领域中指导异腈氰化反应的综合工具。
