Further developments in metal-catalysed C-C bond cleavage in allylic dimethyl malonate derivatives

Article abstract of DOI:10.1016/S0040-4039(96)02510-5

The use of a catalytic amount of nickelbis(1,4-bis(diphenylphosphino)butane in DMF enables the activation of the C-C bond in dimethyl allylmalonate derivatives to proceed under rather smooth reaction conditions, without added nucleophile. Several exmnples like isomerization of substituted-allyl malonate derivatives, racemization of chiral products, but also a synthetic application as an inverse disproportionation reaction are described.