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Título

Pyridine-enhanced head-to-tail dimerization of terminal alkynes by a rhodium-N-heterocyclic-carbene catalyst

AutorRubio-Pérez, Laura ; Azpíroz, Ramón; Giuseppe, Andrea di ; Polo, Víctor; Castarlenas, Ricardo ; Pérez-Torrente, Jesús J. ; Oro, Luis A.
Palabras clavecarbenes
C-C coupling
Dimerization
Rhodium
Alkynes
Fecha de publicación2013
EditorWiley-VCH
CitaciónChemistry - A European Journal 19(45): 15304-15314 (2013)
ResumenA general regioselective rhodium-catalyzed head-to-tail dimerization of terminal alkynes is presented. The presence of a pyridine ligand (py) in a Rh-N-heterocyclic-carbene (NHC) catalytic system not only dramatically switches the chemoselectivity from alkyne cyclotrimerization to dimerization but also enhances the catalytic activity. Several intermediates have been detected in the catalytic process, including the π-alkyne-coordinated RhI species [RhCl(NHC)(η2-HC ≡CCH2Ph)(py)] (3) and [RhCl(NHC){η2-C(tBu) ≡C(E)CH=CHtBu}(py)] (4) and the RhIII-hydride-alkynyl species [RhClH{-C ≡CSi(Me) 3}(IPr)(py)2] (5). Computational DFT studies reveal an operational mechanism consisting of sequential alkyne Ci£ H oxidative addition, alkyne insertion, and reductive elimination. A 2,1-hydrometalation of the alkyne is the more favorable pathway in accordance with a head-to-tail selectivity.
Versión del editorhttp://dx.doi.org/10.1002/chem.201302079
URIhttp://hdl.handle.net/10261/111376
DOI10.1002/chem.201302079
Identificadoresdoi: 10.1002/chem.201302079
issn: 0947-6539
e-issn: 1521-3765
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