Yong-Shou Lin

Study of Pd-elimination under carbonylation conditions: Regioselective formation of esters

Abstract The regioselective synthesis of methyl esters is achieved by carbonylation of two different types of organometallic derivatives resulting from insertion of non-conjugated dienes into a Pd-aryl bond. When the diene and the Pd-aryl synthon [PdPfBr(NCMe)2] (Pf = C6F5) are mixed at low temperature, solutions ofη1-η2-enylpalladium complexes can be isolated and converted into β-aryl methyl esters by reaction with CO in the presence of methanolic solutions of sodium methoxide. When the reactions are carried out at room temperatureη3-allylpalladium complexes are isolated, and their carbonylation gives β,γ-unsaturated esters.