Mechanisms of the Mizoroki–Heck Reaction

The palladium-catalysed Mizoroki–Heck reaction is the most efficient route for the vinylation of aryl/vinyl halides or triflates

Anny Jutand

2009

Scholarcy highlights

  • The palladium-catalysed Mizoroki–Heck reaction is the most efficient route for the vinylation of aryl/vinyl halides or triflates
  • Jutand et al have established that the oxidative addition of PhI to Pd0(OAc)(dppp)− gives the cationic complex PhPd(dppp)(dppp(O))+; this is followed by reaction of iodide ions released from PhI in the course of a catalytic reaction giving PhPdI(dppp) or/and PhPd(OAc)(dppp) whenever acetate ions are used as bases
  • The linear product will be formed if the reaction is performed in the presence of a large excess of anions, as it often occurs in real catalytic reactions, but still via the cationic PhPd(DMF)(dppp)+
  • The Mizoroki–Heck reaction is a subtle and complex reaction which involves a great variety of intermediate palladium complexes
  • The four main steps proposed by Heck have been confirmed. They involved a considerable number of different Pd(0) and Pd(II) intermediates whose structure and reactivity depend on the experimental conditions, namely the catalytic precursor complexes, Pd(OAc)2, palladacycles), the ligand, the additives, the aryl derivatives, the alkenes, which may be ligands for Pd(0) complexes, and at least the base, which can play a
  • Scheme 1.37 Mechanism of the Mizoroki–Heck reaction when the catalytic precursor is Pd(OAc)2 associated with dppp and when the base is not an acetate salt: X = I, R = CO2Me. be the classical oxidative addition of an aryl halide to a Pd(0) complex, as in a classical catalytic cycle involving Pd0/PdII complexes

Need more features? Save interactive summary cards to your Scholarcy Library.