Guangxi Key Laboratory of Electrochemical and Magnetochemical Function Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, P. R. China.
Org Biomol Chem. 2020 Nov 28;18(44):9100-9108. doi: 10.1039/d0ob01838d. Epub 2020 Nov 5.
The cyanation and formylation of imidazo[1,2-a]pyridines were developed under copper-mediated oxidative conditions using ammonium iodide and DMF as a nontoxic combined cyano-group source and DMF as a formylation reagent. Mechanistic studies indicate that the cyanation of imidazo[1,2-a]pyridines proceeds through a two-step sequence: initial iodination and then cyanation. The cyanation has a broad substrate scope and high functional group tolerance, and can be safely conducted on a gram scale. A novel copper-mediated formylation using the widely available DMF as the formylation reagent and environmentally friendly molecular oxygen as the oxidant has also been developed. This protocol also provided a convenient approach for the synthesis of clinically used saripidem.
在铜介导的氧化条件下，使用碘化铵和 DMF 作为无毒的氰基源，DMF 作为甲酰化试剂，发展了咪唑并[1,2-a]吡啶的氰化和甲酰化反应。机理研究表明，咪唑并[1,2-a]吡啶的氰化反应通过两步序列进行：首先碘化，然后氰化。该氰化反应具有广泛的底物范围和高官能团容忍性，并且可以安全地在克级规模上进行。还开发了一种新的铜介导的甲酰化反应，使用广泛可用的 DMF 作为甲酰化试剂和环境友好的分子氧作为氧化剂。该方案还为临床使用的沙利度胺的合成提供了一种便捷的方法。
