Graphite and polymer-supported palladium catalysts, coupled with copper/lithium cocatalysts, have been found very effective for the oxidative carbonylation of unsaturated hydrocarbons. Hex-3-ene-1,6-dioate has been generated in 85% selectivity from 1,3-butadiene, alpha-olefins yield dimethyl succinate derivatives. Butadiene hydrodimerization via analogous platinum catalysis selectively provides 1,6-octadiene, or 2,7-octadienyl formate. Mechanisms for the product selectivity are described.