Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.
Nat Chem. 2011 Apr;3(4):287-90. doi: 10.1038/nchem.1001. Epub 2011 Feb 27.
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 hydroxymethylation.
甲醇是一种丰富的（每年 3500 万吨）可再生化学原料，但作为一碳建筑块在精细化学品合成中的应用还远未得到充分发展。使用我们实验室开发的均相铱催化剂，甲醇与丙二烯直接进行 C-C 偶联，生成含有全碳季碳原子的高醇，没有计量副产物。通过一系列竞争动力学实验证实了一种涉及甲醇氧化的周转限制的催化机制，这是甲醇脱氢的高能量需求的结果。这个过程代表了甲醇的第一个催化 C-C 偶联，提供了羟甲基化的离散产物。
