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00925njm 22002777a 4500 dc Couce-Ríos, A. author Lledós, A. author Fernández López, Israel author Ujaque, G. author 2019-01-01 The reaction mechanism and regioselectivity for the gold(I)-catalyzed hydroamination reaction of terminal alkenes are analyzed by means of density functional theory (DFT) calculations. The influence of the nature of the olefin as well as the ligand present in the gold(I) catalyst on the regioselectivity is investigated. The anti-Markovnikov addition is preferred for some alkenes, particularly those having cyclopropyl or good electron-withdrawing groups in their structures. The regioselectivity of the process is quantitatively analyzed with the help of state-of-the-art computational methods, namely, the activation strain model (ASM) of reactivity and natural orbitals for chemical valence (NOCV) method. It is found that the back-bonding interactions in the initially formed π-complex are directly related to the Gibbs energy barrier difference between the Markonikov and anti-Markovnikov additions. It can be concluded that the coordination mode of the initial π-complex ultimately controls the regioselectivity outcome of the transformation Couce-Rios, Almudena, et al. «Origin of the Anti-Markovnikov Hydroamination of Alkenes Catalyzed by L–Au(I) Complexes: Coordination Mode Determines Regioselectivity». ACS Catalysis, vol. 9, n.o 2, febrero de 2019, pp. 848-58. 10.1021/acscatal.8b03843 https://hdl.handle.net/20.500.14352/114713 https://pubs.acs.org/doi/10.1021/acscatal.8b03843 Origin of the Anti-Markovnikov Hydroamination of Alkenes Catalyzed by L−Au(I) Complexes: Coordination Mode Determines Regioselectivity