The methoxycarbonylation of aryl chlorides catalysed by palladium complexes of bis(di-tert-butylphosphinomethyl)benzene

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.