Letter

Remote carboxylation of halogenated aliphatic hydrocarbons with carbon dioxide

Received:
Accepted:
Published online:

Abstract

Catalytic carbon–carbon bond formation has enabled the streamlining of synthetic routes when assembling complex molecules1. It is particularly important when incorporating saturated hydrocarbons, which are common motifs in petrochemicals and biologically relevant molecules. However, cross-coupling methods that involve alkyl electrophiles result in catalytic bond formation only at specific and previously functionalized sites2. Here we describe a catalytic method that is capable of promoting carboxylation reactions at remote and unfunctionalized aliphatic sites with carbon dioxide at atmospheric pressure. The reaction occurs via selective migration of the catalyst along the hydrocarbon side-chain3 with excellent regio- and chemoselectivity, representing a remarkable reactivity relay when compared with classical cross-coupling reactions. Our results demonstrate that site-selectivity can be switched and controlled, enabling the functionalization of less-reactive positions in the presence of a priori more reactive ones. Furthermore, we show that raw materials obtained in bulk from petroleum processing, such as alkanes and unrefined mixtures of olefins, can be used as substrates. This offers an opportunity to integrate a catalytic platform en route to valuable fatty acids by transforming petroleum-derived feedstocks directly4.

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Acknowledgements

We are grateful for financial support provided by ICIQ, the European Research Council (ERC-StG-277883 and ERC-2015-PoC-713577), MINECO (CTQ2015-65496-R and Severo Ochoa Excellence Accreditation 2014-2018, SEV-2013-0319) and the Cellex Foundation. F.J.-H. and J.C. thank COFUND and Marie Curie Actions for an Intra-European Fellowship (FP7-PEOPLE-2012-IEF-328381).

Author information

Affiliations

  1. Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avinguda Països Catalans 16, 43007 Tarragona, Spain

    • Francisco Juliá-Hernández
    • , Toni Moragas
    • , Josep Cornella
    •  & Ruben Martin
  2. ICREA, Passeig Lluïs Companys 23, 08010 Barcelona, Spain

    • Ruben Martin

Authors

  1. Search for Francisco Juliá-Hernández in:

  2. Search for Toni Moragas in:

  3. Search for Josep Cornella in:

  4. Search for Ruben Martin in:

Contributions

F.J.-H., T.M. and J.C. performed and analysed the experiments. R.M. wrote the manuscript. All authors commented on the final manuscript and contributed to the analysis and interpretation of the results.

Competing interests

A European patent application to ICIQ and ICREA was filed, with application number EP16382336.

Corresponding author

Correspondence to Ruben Martin.

Reviewer Information Nature thanks I. Marek and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

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    Supplementary Information

    This file contains Supplementary Text and Data, including a detailed description of the methods utilized, characterization of all compounds and spectroscopical data – see contents page for details.

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