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

Abstract

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

Industrially applied and relevant transformations of 1,3-butadiene using homogeneous catalysts

“…In addition, the catalytic system was also effective for the conversion of numerous other nucleophiles. 177,[182][183][184][185] With respect to the industrial realization of such a process, it is important to note that apart from the technical success, the implementation of such a methodology will strongly depend on the development of the different feedstock prices (e.g. benzene versus 1,3-butadiene).…”

Pd-catalysed synthesis of oxomalonamides through adjacent triple carbonylation of tertiary amines

“…7 The Fischer–Tropsch process serves as an exceptional example to yield carbon chain (C4–C10) products through controlled homologation and hydrogenation of CO. 8 Moreover, double carbonylation at adjacent or distant positions can be accomplished under certain conditions. 9 Adjacent double carbonylation has received great interest as they form oxamates, α-keto amides, and oxamides, which are useful natural products and pharmaceuticals. 10…”