Metal-Free Synthesis of 3‑Arylquinolin-2-ones from Acrylic Amides via a Highly Regioselective 1,2-Aryl Migration: An Experimental and Computational Study

Combined experimental and theoretical investigations into the phenyliodine bis­(trifluoro­acetate) (PIFA)-mediated reaction of N-arylcinnamamide to produce 3-arylquinolin-2-one derivatives have been conducted. High regioselectivity during the aryl migration process was observed in 3,3-disubstituted acrylamides. Density functional theory calculation was conducted in an attempt to understand the mechanism and the origin of the regioselectivity. On the basis of both the experimental and the theoretical results, a mechanism involving an oxidative annulation, followed by an aryl migration, has been proposed. The annulation is the regioselectivity determining step.

本研究结合实验与理论手段，对二(三氟乙酸)碘苯（phenyliodine bis(trifluoroacetate), PIFA）介导的N-芳基肉桂酰胺合成3-芳基喹啉-2-酮衍生物的反应开展了系统探究。在3,3-二取代丙烯酰胺类底物的芳基迁移过程中，观测到了较高的区域选择性。为阐明该反应的机理及区域选择性的起源，本研究进行了密度泛函理论计算。基于实验与理论结果，本研究提出了一条包含氧化环化、随后芳基迁移的反应机理，其中环化步骤为区域选择性的决定步骤。