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

• Published in: Journal of organic chemistry Vol. 81; no. 10; pp. 4058 - 4065
• Main Authors: Liu, Le, Zhang, Tonghuan, Yang, Yun-Fang, Zhang-Negrerie, Daisy, Zhang, Xinhao, Du, Yunfei, Wu, Yun-Dong, Zhao, Kang
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 20.05.2016; Amer Chemical Soc
• Subjects: acrylamides; chemical reactions; chemical structure; Chemistry; Chemistry, Organic; methodology; organic chemistry; Physical Sciences; regioselectivity; Science & Technology; ACTIVATED ALKENES; MOLECULAR-ORBITAL METHODS; EFFICIENT SYNTHESIS; CHEMISTRY; OXINDOLES; BOND FORMATION; IODINE; BASIS-SETS; C-H FUNCTIONALIZATION; CYCLIZATION
• ISSN: 0022-3263; 1520-6904; 1520-6904
• DOI: 10.1021/acs.joc.6b00345

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.