Dalian Institute of Chemical Physics, Chinese Academy of Sciences , 457 Zhongshan Road , Dalian 116023 , People's Republic of China.
University of Chinese Academy of Sciences , Beijing 100049 , People's Republic of China.
J Org Chem. 2019 Feb 15;84(4):2083-2092. doi: 10.1021/acs.joc.8b03092. Epub 2019 Feb 5.
Rhodium(III)-catalyzed annulation of acetophenone O-acetyl oximes with allenoates was achieved, affording isoquinolines in good to excellent yields with high regioselectivities under redox-neutral conditions. Allenoates acted as the C2 synthons in the annulation reaction. The present synthetic methodology features good functional group tolerance and avoids metal salts as the external oxidants. The proposed mechanism suggests that the reaction proceeds through arene C-H activation, allene insertion, and C-N coupling.
铑(III)催化的苯乙酮 O-乙酰肟与丙二烯酸酯的环化反应得以实现，在氧化还原中性条件下以良好到优秀的收率和高区域选择性得到异喹啉。丙二烯酸酯在环化反应中充当 C2 合成子。本合成方法具有良好的官能团容忍性，避免了使用金属盐作为外部氧化剂。提出的反应机理表明，反应经过芳环 C-H 活化、丙二烯插入和 C-N 偶联。
