Manganese(I)-Catalyzed C-H Aminocarbonylation of Heteroarenes

• Published in: Angewandte Chemie (International ed.) Vol. 54; no. 47; pp. 14137 - 14140
• Main Authors: Liu, Weiping, Bang, Jonas, Zhang, Yujiao, Ackermann, Lutz
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 16.11.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: C-H activation; Chemistry; Chemistry, Multidisciplinary; indoles; isocyanates; manganese; Physical Sciences; reaction mechanisms; Science & Technology; OXIDATION; ARYLATIONS; ALKYLATION; reaction mechanisms; AMIDATION; FLUORINATION; manganese; FUNCTIONALIZATION; indoles; C-H activation; isocyanates; BOND ACTIVATION; ARYL; CYCLIZATION
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201507087

A versatile manganese(I) catalyst was employed in CH aminocarbonylation reactions of heteroarenes with aryl as well as with alkyl isocyanates using a removable directing group approach. Detailed experimental mechanistic studies were suggestive of an organometallic CH manganesation step, followed by a rate‐determining migratory insertion. Heteroaromatic amides were obtained by a step‐economical, manganese(I)‐catalyzed CH aminocarbonylation reaction between heteroarenes and aryl and alkyl isocyanates. The catalytic cycle was initiated by a facile organometallic CH manganesation step, followed by a rate‐determining migratory insertion. DG = directing group.