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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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.
The authors declare no competing financial interests.
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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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