ELKH-PTE Research Group for Selective Chemical Syntheses, Ifjúság u. 6, Pécs H-7624, Hungary.
János Szentágothai Research Centre, University of Pécs, Ifjúság u. 20, Pécs H-7624, Hungary.
J Org Chem. 2023 Apr 21;88(8):5172-5179. doi: 10.1021/acs.joc.2c02712. Epub 2023 Apr 13.
Palladium-catalyzed amino- and alkoxycarbonylation reactions of aryl iodides were investigated in the presence of aliphatic heterobifunctional N,O-nucleophiles. Selective synthesis of amide alcohols and amide esters was realized, controlled by the base and substrate ratio. The effect of iodobenzene substituents was also studied with surprising results in terms of product selectivity. In addition to the model ethanolamine/iodobenzene system, various heteroaromatic substrates and numerous related nucleophiles were tested under optimized conditions, providing moderate to good yields of the target compounds. Reactions of serinol and 1,3-diamino-2-propanol as model trifunctional compounds showed particularly high chemoselectivity on amide ester products. Considering the coordinative properties of the applied nucleophiles, a rational catalytic cycle was proposed.
钯催化的芳基碘的氨基和烷氧基羰基化反应在脂肪族杂双功能 N,O-亲核试剂的存在下进行。通过控制碱和底物的比例，实现了酰胺醇和酰胺酯的选择性合成。还研究了碘苯取代基的影响，其在产物选择性方面的结果出人意料。除了模型乙醇胺/碘苯体系外，还在优化条件下测试了各种杂芳基底物和许多相关的亲核试剂，得到了中等至良好收率的目标化合物。丝氨酸和 1,3-二氨基-2-丙醇作为模型三功能化合物的反应对酰胺酯产物表现出特别高的化学选择性。考虑到应用亲核试剂的配位性质，提出了一个合理的催化循环。
