Dasgupta, AyanGuerzoni, Michael G.Alotaibi, Nusaybahvan Ingen, YaraFarshadfar, KavehRichards, EmmaAriafard, AlirezaMelen, Rebecca L.2025-12-162025-12-162044-4753ORCID:/0000-0003-2383-6380/work/198195205https://hdl.handle.net/1885/733795501The efficacy of boron-based catalysts has drawn considerable attention from the scientific community due to their relatively low toxicities and high selectivities. Formation of a new carbon-carbon or carbon-nitrogen bond to generate an amide/urea functionality using mild, catalytic reaction protocols has always been an important challenge, as functionalised amides and urea derivatives are important scaffolds in medicinal chemistry. Herein we report a facile and mild catalytic reaction protocol towards the amidation of N-methyl indoles/pyrroles (17 examples, yields up to 58%) using B(C6F5)3 (30 mol%). Moreover, our investigation revealed that although catalytic amounts of B(C6F5)3 (10 mol%) are efficient towards the N-carboxamidation of unprotected indoles, catalytic BCl3 (5 mol%) is capable of producing near quantitative yields of the N-carboxamidation products (21 examples, yields up to 95%). In contrast with previous literature reports, the reaction between 2-(alkynyl)anilines and aryl isocyanates using catalytic BCl3 (5 mol%) afforded N-H inserted products (9 examples, yields up to 71%) chemo-selectively as opposed to the intramolecular hydroamination product. Comprehensive DFT studies have been undertaken to understand the mechanistic details of the N-H functionalisation of indoles.A. D. G., M. G. G., E. R., and R. L. M. would like to acknowledge the Leverhulme Trust for funding (RPG-2020-016). N. A. acknowledges support from the Saudi Ministry of Education and the King Faisal University, Saudi Arabia. A. A. and K. F. thank the Australian Research Council (ARC) for project funding (DP180100904) and the Australian National Computational Infrastructure and the University of Tasmania for the generous allocation of computing time. R. L. M. would like to thank the EPSRC for a research Fellowship (EP/R026912/1). R. L. M. would like to thank Universities Wales for Global Wales International Research Mobility funding (UNIW/RMF-CU/08).9enPublisher Copyright: © 2022 The Royal Society of Chemistry.2022-08-2510.1039/d2cy01441f85138133251