Multiple Roles of the Pyrimidyl Group in the Rhodium-Catalyzed Regioselective Synthesis and Functionalization of Indole-3-carboxylic Acid Esters

• Published in: Advanced synthesis & catalysis Vol. 358; no. 2; pp. 188 - 194
• Main Authors: Jiang, Hui, Gao, Shang, Xu, Jinyi, Wu, Xiaoming, Lin, Aijun, Yao, Hequan
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 21.01.2016; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Aniline; Bonding; Carboxylic acids; Catalysis; Chemical synthesis; Chemistry; Chemistry, Applied; Chemistry, Organic; CH activation; diazo compounds; Esters; Functional groups; indole-3-carboxylic acid esters; Indoles; Physical Sciences; pyrimidyl group; Regioselectivity; Rhodium; rhodium catalysis; Science & Technology; Strategy; Synthesis; Tolerances; ACTIVATION; indole-3-carboxylic acid esters; DIAZO-COMPOUNDS; C-H FUNCTIONALIZATION; rhodium catalysis; INDOLES; QUINOLINE N-OXIDES; C-H activation; C-8 POSITION; pyrimidyl group; INTRAMOLECULAR AMINATION; RH(III)-CATALYZED SYNTHESIS; diazo compounds; BOND; CARBENOID FUNCTIONALIZATION
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201500769

A regioselective synthesis of indole‐3‐carboxylic acid esters from anilines and diazo compounds has been realized by making use of the pyrimidyl group‐assisted rhodium‐catalyzed CH activation and CN bond formation. The reaction proceeds under mild conditions, exhibits good functional group tolerance and scalability. Reutilization of the pyrimidyl directing group in the resulting products provided an efficient strategy for further C‐7 functionalization of indoles. Moreover, the pyrimidyl moiety could be readily removed as a leaving group to offer various free NH indoles.