The scope and mechanism of palladium-catalysed Markovnikov alkoxycarbonylation of alkenes

Haoquan Li, Kaiwu Dong, Haijun Jiao, Helfried Neumann, Ralf Jackstell, Matthias Beller

Research output: Contribution to journalArticlepeer-review

106 Scopus citations

Abstract

Hydroesterification reactions represent a fundamental type of carbonylation reaction and constitute one of the most important industrial applications of homogeneous catalysis. Over the past 70 years, numerous catalyst systems have been developed that allow for highly linear-selective (anti-Markovnikov) reactions and are used in industry to produce linear carboxylates starting from olefins. In contrast, a general catalyst system for Markovnikov-selective alkoxycarbonylation of aliphatic olefins remains unknown. In this paper, we show that a specific palladium catalyst system consisting of PdX2/N-phenylpyrrole phosphine (X, halide) catalyses the alkoxycarbonylation of various alkenes to give the branched esters in high selectivity (branched selectivity up to 91%). The observed (and unexpected) selectivity has been rationalized by density functional theory computation that includes a dispersion correction.

Original languageEnglish
Pages (from-to)1159-1166
Number of pages8
JournalNature Chemistry
Volume8
Issue number12
DOIs
StatePublished - 1 Dec 2016
Externally publishedYes

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