J. Moran, Angelika Preetz, Ryan A. Mesch
Feb 27, 2011
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Journal
Nature Chemistry
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. Methanol is an abundant, renewable chemical feedstock. Here, a homogenous iridium catalyst enables a byproduct-free C–C coupling of methanol and allenes, producing higher alcohols that incorporate all-carbon quaternary centres. This process represents the first catalytic C–C coupling of methanol to provide discrete products of hydrohydroxymethylation.