Pan Mengni, Shen Yue, Li Yang, Shen Chaoren, Li Wanfang
School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, P. R. China.
School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, P. R. China.
J Org Chem. 2024 Jun 21;89(12):8656-8667. doi: 10.1021/acs.joc.4c00591. Epub 2024 Jun 3.
The nucleophilic ring-opening of aziridine derivatives provides an important synthetic tool for the preparation of various β-functionalized amines. Amines as nucleophiles are employed to prepare synthetically useful 1,2-diamines in the presence of various catalysts or activators. Herein, the B(OH)-mediated reductive ring-opening transformation of -tosyl aziridines by nitroarenes was developed. This aqueous protocol employed nitroarenes as cheap and readily available amino sources and proceeds under external catalyst-free conditions. Control experiments and DFT calculations pointed to the reduction of nitroarenes to aryl amines via -aryl boramidic acid () and an S1-type ring-opening of -tosylaziridines by the resultant aryl amines with high regioselectivity.
氮杂环丙烷衍生物的亲核开环反应为制备各种β-官能化胺提供了一种重要的合成工具。胺作为亲核试剂，在各种催化剂或活化剂存在下用于制备具有合成价值的1,2-二胺。在此，开发了硼（OH）介导的对甲苯磺酰基氮杂环丙烷与硝基芳烃的还原开环转化反应。该水相反应使用硝基芳烃作为廉价且易于获得的氨基源，并且在无外部催化剂的条件下进行。对照实验和密度泛函理论计算表明，硝基芳烃通过芳基硼酸酰胺还原为芳基胺，并由所得芳基胺以高区域选择性对甲苯磺酰基氮杂环丙烷进行S1型开环反应。
