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Iridium-catalysed direct C–C coupling of methanol and allenes

Nature Chemistry volume 3, pages 287–290 (2011)Cite this article

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Abstract

Methanol is an abundant (35 million metric tons per year), renewable chemical feedstock, yet its use as a one-carbon building block in fine chemical synthesis is highly underdeveloped. Using a homogeneous iridium catalyst developed in our laboratory, methanol engages in a direct C–C coupling with allenes to furnish higher alcohols that incorporate all-carbon quaternary centres, free of stoichiometric by-products. A catalytic mechanism that involves turnover-limiting methanol oxidation, a consequence of the high energetic demand of methanol dehydrogenation, is corroborated through a series of competition kinetics experiments. This process represents the first catalytic C–C coupling of methanol to provide discrete products of hydrohydroxymethylation.

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Figure 1: Mechanism for the iridium-catalysed C–C coupling of methanol and the structure of DPPF-I.
Figure 2: Deuterium labelling and competition kinetics experiments.

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Acknowledgements

Acknowledgement is made to the Robert A. Welch Foundation (F-0038), the Texas Higher Education Coordinating Board (NHARP Award 01849), the University of Texas Center for Green Chemistry and Catalysis and the National Science Foundation (CHE-1021640). The Natural Sciences and Engineering Research Council of Canada and the German Research Foundation are thanked for partial support of J.M. and A.P., respectively.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, 78712, Texas, USA

    Joseph Moran, Angelika Preetz, Ryan A. Mesch & Michael J. Krische

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Contributions

J.M., A.P. and R.A.M. carried out the experiments. M.J.K. directed the study. M.J.K. and J.M. co-wrote the manuscript.

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Correspondence to Michael J. Krische.

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Crystallographic data for compound DPPF-I (CIF 69 kb)

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Moran, J., Preetz, A., Mesch, R. et al. Iridium-catalysed direct C–C coupling of methanol and allenes. Nature Chem 3, 287–290 (2011). https://doi.org/10.1038/nchem.1001

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