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Direct synthesis of adipic acid esters via palladium-catalyzed carbonylation of 1,3-dienes

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Science  20 Dec 2019:
Vol. 366, Issue 6472, pp. 1514-1517
DOI: 10.1126/science.aaz1293

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A carbonylation path to a nylon precursor

Adipic acid and its esters are manufactured on a massive scale, primarily to produce nylon. However, the standard route requires large quantities of corrosive nitric acid. J. Yang et al. present an efficient alternative route whereby a palladium catalyst adds carbon monoxide to each end of butadiene (see the Perspective by Schaub). Both reactants are available at commodity scale, and the reaction produces no by-products. An optimized bidentate phosphine ligand bearing a pyridine substituent for proton shuttling proved key to attaining the necessary selectivity.

Science, this issue p. 1514; see also p. 1447

Abstract

The direct carbonylation of 1,3-butadiene offers the potential for a more cost-efficient and environmentally benign route to industrially important adipic acid derivatives. However, owing to the complex reaction network of regioisomeric carbonylation and isomerization pathways, a selective practical catalyst for this process has thus far proven elusive. Here, we report the design of a pyridyl-substituted bidentate phosphine ligand (HeMaRaphos) that, upon coordination to palladium, catalyzes adipate diester formation from 1,3-butadiene, carbon monoxide, and butanol with 97% selectivity and 100% atom-economy under industrially viable and scalable conditions (turnover number > 60,000). This catalyst system also affords access to a variety of other di- and triesters from 1,2- and 1,3-dienes.

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