Origin of the Anti-Markovnikov Hydroamination of Alkenes Catalyzed by L-Au(I) Complexes : Coordination Mode Determines Regioselectivity
Couce-Rios, Almudena (Universitat Autònoma de Barcelona. Departament de Química)
Lledós, Agustí (Universitat Autònoma de Barcelona. Departament de Química)
Fernández, Israel (Universitat Autònoma de Barcelona. Departament de Química)
Ujaque Pérez, Gregori (Universitat Autònoma de Barcelona. Departament de Química)

Data:	2019
Resum:	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.
Ajuts:	Agencia Estatal de Investigación CTQ2017-87889-P Ministerio de Economía y Competitividad CTQ2016-78205-P Ministerio de Economía y Competitividad CTQ2016-81797-REDC
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Llengua:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Matèria:	Anti-Markovnikov ; ASM-EDA(NOCV) analysis ; DFT calculations ; Gold ; Hydroamination
Publicat a:	ACS catalysis, Vol. 9, Issue 2 (February 2019) , p. 848-858, ISSN 2155-5435

DOI: 10.1021/acscatal.8b03843

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