The mechanism of the N-alkylation of amines with alcohols[1] catalyzed by an iridium complex containing an N-heterocyclic carbene (NHC) ligand with a tethered alcohol / alkoxide functionality has been investigated in detail by a combination of experimental and computational methods.[2] Here we will present insights into the mechanism obtained from DFT calculations, Hammett studies and isotopic labeling experiments under competitive and non-competitive conditions, as well as from kinetic investigations.[3] [1] For recent reviews and perspective articles, see: (a) Guillena, G.; Ramón, D. J.; Yus, M. Chem. Rev. 2010, 110, 1611-1641. (b) Dobereiner, G. E.; Crabtree, R. H. Chem. Rev. 2010, 110, 681-703. (c) Watson, A. J. A.; Williams, J. M. J. Science, 2010, 329, 635-636. (d) Bähn, S.; Imm, S.; Neubert, L.; Zhang, M.; Neumann, H.; Beller, M. ChemCatChem 2011, 3, 1853-1864. (e) Pan, S.; Shibata, T. ACS Cat. 2013, 3, 704-712. [2] Bartoszewicz, A.; Marcos, R.; Sahoo, S.; Inge, A. K.; Zou, X.; Martín-Matute, B. Chem. Eur. J. 2012, 18, 14510-14519. [3] Bartoszewicz, A.; González Miera, G.; Marcos, R.; Norrby, P.-O.; Martín-Matute, B. ACS Catal. 2015, 5, 3704-3716

Insights into a bifunctional iridium complex-promoted N-alkylation of amines with alcohol

251st National Meeting (2016)

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