title: The methoxycarbonylation of aryl chlorides catalysed by palladium complexes of bis(di-tert-butylphosphinomethyl)benzene.
abstract: A catalyst system based on palladium-1,2-bis-(di-tert-butylphosphinomethyl)benzene (BDTBPMB) shows good activity for the methoxycarbonylation of strongly activated aryl chlorides, like 4-chloromethylbenzoate or 4-chlorocyanobenzene. Surprisingly, the use of less activated aryl chlorides, like 4-chloroacetophenone, leads to the formation of dimethyl terephthalate amongst other products arising from organic reactions of methoxide ion and/or CO. Less nucleophilic alcohols such as 2,2,2-trifluoroethanol promote the formation of carbonylation products even from 4-chloroacetophenone and chlorobenzene. Labelling studies involving CD3OH, CD3OD or 13CO give information on the origin of many of the products.
authors.affiliation: School of Chemistry, University of St. Andrews, St. Andrews, Fife, UK KY16 9ST.
authors.forename: Cristina
authors.initials: C
authors.lastname: Jimenez-Rodriguez
authors.forename: Graham R
authors.initials: GR
authors.lastname: Eastham
authors.forename: David J
authors.initials: DJ
authors.lastname: Cole-Hamilton