The catalytic activity of eta(2)-(olefin)palladium(O)(iminophosphine) complexes in the Suzuki-Miyaura coupling is strongly dependent on the reaction conditions and on the nature of the ligands. The reaction is at the best carried out in aromatic solvents in the presence of K2CO3 at 90-110 degrees C. Higher reaction rates are obtained when the R substituent on the N-imino group is an aromatic group of low steric hindrance and the olefin is a moderate pi-accepting ligand such as dimethyl fumarate. At temperatures lower than 90 degrees C, a self-catalyzed process leading to catalyst deactivation becomes predominant. Preliminary mechanistic investigations indicate that the oxidative addition of the aryl bromide to a Pd(O) species is the rate determining step in the catalytic cycle and that the olefin plays a key role in catalyst stabilization. Systems in situ prepared by mixing Pd(OAc)(2) or Pd(dba)(2) with 1 equiv of iminophosphine appear substantially less active than the preformed catalysts. (c) 2005 Elsevier Ltd. All rights reserved.

Scrivanti, A., Beghetto, V., Matteoli, U., Antonaroli, S., Marini, A., Crociani, B. (2005). Catalytic activity of eta(2)-(olefin)palladium(0) complexes with iminophosphine ligands in the Suzuki-Miyaura reaction. Role of the olefin in the catalyst stabilization. TETRAHEDRON, 61(41), 9752-9758 [10.1016/j.tet.2005.06.079].

Catalytic activity of eta(2)-(olefin)palladium(0) complexes with iminophosphine ligands in the Suzuki-Miyaura reaction. Role of the olefin in the catalyst stabilization

ANTONAROLI, SIMONETTA;CROCIANI, BRUNO
2005-06-24

Abstract

The catalytic activity of eta(2)-(olefin)palladium(O)(iminophosphine) complexes in the Suzuki-Miyaura coupling is strongly dependent on the reaction conditions and on the nature of the ligands. The reaction is at the best carried out in aromatic solvents in the presence of K2CO3 at 90-110 degrees C. Higher reaction rates are obtained when the R substituent on the N-imino group is an aromatic group of low steric hindrance and the olefin is a moderate pi-accepting ligand such as dimethyl fumarate. At temperatures lower than 90 degrees C, a self-catalyzed process leading to catalyst deactivation becomes predominant. Preliminary mechanistic investigations indicate that the oxidative addition of the aryl bromide to a Pd(O) species is the rate determining step in the catalytic cycle and that the olefin plays a key role in catalyst stabilization. Systems in situ prepared by mixing Pd(OAc)(2) or Pd(dba)(2) with 1 equiv of iminophosphine appear substantially less active than the preformed catalysts. (c) 2005 Elsevier Ltd. All rights reserved.
Pubblicato
Rilevanza internazionale
Articolo
Sì, ma tipo non specificato
Settore CHIM/07 - Fondamenti Chimici delle Tecnologie
English
Con Impact Factor ISI
Arylboronic acids; Biaryls; Cross-coupling; Iminophosphine complexes; Palladium; Suzuki-Miyaura reaction
Scrivanti, A., Beghetto, V., Matteoli, U., Antonaroli, S., Marini, A., Crociani, B. (2005). Catalytic activity of eta(2)-(olefin)palladium(0) complexes with iminophosphine ligands in the Suzuki-Miyaura reaction. Role of the olefin in the catalyst stabilization. TETRAHEDRON, 61(41), 9752-9758 [10.1016/j.tet.2005.06.079].
Scrivanti, A; Beghetto, V; Matteoli, U; Antonaroli, S; Marini, A; Crociani, B
Articolo su rivista
File in questo prodotto:
File Dimensione Formato  
Tetrahedron. 2005.pdf

accesso aperto

Descrizione: Articolo Principale
Dimensione 154.91 kB
Formato Adobe PDF
154.91 kB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/23670
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? 37
social impact