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

Nature Chemistry volume 8, pages 1159–1166 (2016)Cite this article

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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.

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Figure 1: Challenges and application potentials for the palladium-catalysed Markovnikov alkoxycarbonylation of alkenes.
Figure 2: Markovnikov alkoxycarbonylation of 1-octene using a range of different ligands.
Figure 3: DFT calculations.

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Acknowledgements

The Federal Ministry of Education and Research (BMBF) and Evonik Industries are acknowledged for their general support. K.D. acknowledges a Shanghai Institute of Organic Chemistry-Zhejiang Medicine joint fellowship for financial support. The analytic department of LIKAT is acknowledged. We are thankful to Q. Liu and X. Fang for the helpful and supportive discussions.

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Authors and Affiliations

  1. Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein Straße 29a, Rostock, 18059, Germany

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

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  1. Haoquan Li
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Contributions

M.B. and H.L. conceived and designed the experiments. H.L. and K.D. performed the experiments and analysed the data. H.J. performed the DFT study. H.N. and R.J. participated in the discussions and supported the project. M.B., H.J. and H.L. co-wrote the paper.

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Correspondence to Matthias Beller.

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The authors declare no competing financial interests.

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Crystallographic data for compound L15_2_PdCl2. (CIF 941 kb)

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Li, H., Dong, K., Jiao, H. et al. The scope and mechanism of palladium-catalysed Markovnikov alkoxycarbonylation of alkenes. Nature Chem 8, 1159–1166 (2016). https://doi.org/10.1038/nchem.2586

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