Efficient Palladium?Catalyzed Carbonylation of 1,3?Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters

The dicarbonylation of 1,3-butadiene to adipic acid derivatives offers the potential for a more cost-efficient and environmentally benign industrial process. However, complex reaction network regioisomeric carbonylation isomerization pathways, make selective direct transformation particularly difficult. Here, we report surprising solvent effects on this palladium-catalysed process in presence 1,2-bis-di-tert-butylphosphin-oxylene (dtbpx) ligands, which allow adipate diester formation from 1,3-butadiene, carbon monoxide, methanol with 97 % selectivity 100 atom-economy under scalable conditions. Under optimal conditions variety di- triesters 1,2- 1,3-dienes can be obtained good excellent yields.