Ferrocene-based palladacyclic precatalysts for C-C bond forming reactions

ORGN 90

Christopher J. Richards and Francesc X. Roca. Department of Chemistry, Queen Mary, University of London, Mile End Road, London, NA, United Kingdom
Starting from 2-bromophenylferrocene (1), monophosphine ligands (2) are readily prepared by bromo-lithium exchange followed by addition of ClPR2. On combining with palladium acetate these metallocenes are rapidly palladated (e.g. with R=Cy, the reaction is essentially complete within 10 min at RT in toluene) to give palladacycles (3) as air-stable and easily handled complexes. The palladacycles are very effective precatalysts for the Suzuki reaction of aryl chlorides. For example with R=Cy, as little as 0.01 mol% of complex (3) results in efficient cross-coupling between 2-chlorotoluene and phenylboronic acid at 60 °C. Further examples of the use of these palladacycles in catalysis will be described.