Mechanistic Insights on the Hydration of Terminal and Internal Allenes Catalyzed by [(NHC)Au]+
Muñoz-López, Sara (Universitat Autònoma de Barcelona. Departament de Química)
Couce-Rios, Almudena (Universitat Autònoma de Barcelona. Departament de Química)
Sciortino, Giuseppe (Universitat Autònoma de Barcelona. Departament de Química)
Lledós, Agustí (Universitat Autònoma de Barcelona. Departament de Química)
Ujaque Pérez, Gregori (Universitat Autònoma de Barcelona. Departament de Química)

Date:	2018
Abstract:	The reaction mechanism for the hydration of internal and terminal allenes catalyzed by [Au(NHC)]+ is analyzed by means of DFT calculations. Several reaction pathways for generating the two possible regioisomers were evaluated. Direct addition on coordinated allenes or to an intermediate with a σ-allylic cation structure as suggested for the Au(I)-catalyzed hydroamination of allenes were considered. The isomerization between both regioisomeric products catalyzed by the same Au(I) catalyst was also investigated as suggested for hydroalkoxylation of allenes. The regioselectivity of the reaction predicted by computation agrees with experiment for both terminal and internal allenes. The presence of alkyl or aryl substituents introduces differences in the reaction mechanism for the hydration process.
Grants:	Agencia Estatal de Investigación CTQ2017-87889-P Ministerio de Economía y Competitividad CTQ2016-81797-REDC
Rights:	Tots els drets reservats.
Language:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Published in:	Organometallics, Vol. 37, Issue 20 (October 2018) , p. 3543-3551, ISSN 1520-6041

DOI: 10.1021/acs.organomet.8b00230

Postprint 10 p, 583.6 KB

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