Mechanism of the Stille reaction catalyzed by palladium ligated to arsine ligand: PhPdl(AsPh3)(DMF) is the species reacting with vinylstannane in DMF

  • Amatore C
  • Bahsoun A
  • Jutand A
 et al. 
  • 23

    Readers

    Mendeley users who have this article in their library.
  • 124

    Citations

    Citations of this article.

Abstract

The kinetics of the reaction of PhPdI(AsPh(3))(2) (formed via the fast oxidative addition of PhI with Pd(0)(AsPh(3))(2)) with a vinyl stannane CH(2)[double bond]CH[bond]Sn(n-Bu)(3) has been investigated in DMF. This reaction (usually called transmetalation step) is the prototype of the rate determining second step of the catalytic cycle of Stille reactions. It is established here that the transmetalation proceeds through PhPdI(AsPh(3))(DMF), generated by the dissociation of one ligand AsPh(3) from PhPdI(AsPh(3))(2). PhPdI(AsPh(3))(DMF) is the reactive species, which leads to styrene through its reaction with CH(2)[double bond]CH[bond]SnBu(3). Consequently, in DMF, the overall nucleophilic attack mainly proceeds via a mechanism involving PhPdI(AsPh(3))(DMF) as the central reactive complex and not PhPdI(AsPh(3))(2). The dimer [Ph(2)Pd(2)(mu(2)-I)(2)(AsPh(3))(2)] has been independently synthesized and characterized by its X-ray structure. In DMF, this dimer dissociates quantitatively into PhPdI(AsPh(3))(DMF), which reacts with CH(2)[double bond]CH[bond]SnBu(3). The rate constant for the reaction of PhPdI(AsPh(3))(DMF) with CH(2)[double bond]CH[bond]SnBu(3) has been determined in DMF for each situation and was found to be comparable.

Get free article suggestions today

Mendeley saves you time finding and organizing research

Sign up here
Already have an account ?Sign in

Find this document

Authors

  • Christian Amatore

  • Ali A. Bahsoun

  • Anny Jutand

  • Gilbert Meyer

  • Alexandre Ndedi Ntepe

  • Louis Ricard

Cite this document

Choose a citation style from the tabs below

Save time finding and organizing research with Mendeley

Sign up for free