Selective Palladium-catalyzed synthesis of Diesters: Alkoxycarbonylation of a CO2-butadiene derived ?-lactone

The development of sustainable processes for chemical synthesis, energy and petrochemical technologies is one of the major challenges and noteworthy task for 21sr century. Notably, catalysis is a key technology for achieving more sustainable processes in the chemical, pharmaceutical and material industries. Currently, more than 80% of all chemical products are made via catalysis. In this regard, the development of more selective, cost-effective and durable catalysts constitutes a key factor for the production of all kinds of chemicals today and in the future.

Novel unsaturated C10 diesters are produced via alkoxycarbonylation of ?-lactone 1 (3- ethylidene-6-vinyltetrahydro2H-pyran-2-one), derived from the telomerization of CO2 and butadiene. Key for the selective valorization of 1 is the use of a catalytic system based on PdCl2, a chelating phosphine bearing electron-withdrawing groups and an acidic promoter. The unsaturated C10 methyl diester can be easily hydrogenated on Pd/C under mild conditions to afford its corresponding saturated diester. Subsequent hydrogenation using the homogeneous [Ru(acac)3]/Triphos catalysts gives 2- ethyloctane-1,8-diol in high yield. The overall procedure allows synthesizing new building blocks for the manufacturing of renewable polymers and polymers processing materials.