Laboratory of Organic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, Zurich, Switzerland.
Nat Commun. 2023 May 5;14(1):2604. doi: 10.1038/s41467-023-38305-y.
Oxygenated molecules are omnipresent in natural as well as artificial settings making the redox transformation of the present C-O bonds a central tool for their processing. However, the required (super)stoichiometric redox agents which traditionally include highly reactive and hazardous reagents pose multiple practical challenges including process safety hazards or special waste management requirements. Here, we report a mild Ni-catalyzed fragmentation strategy based on carbonate redox tags for redox transformations of oxygenated hydrocarbons in the absence of any external redox equivalents or other additives. The purely catalytic process enables the hydrogenolysis of strong C(sp)-O bonds including that of enol carbonates as well as the catalytic oxidation of C-O bonds under mild conditions down to room temperature. Additionally, we investigated the underlying mechanism and showcased the benefits of carbonate redox tags in multiple applications. More broadly, the work herein demonstrates the potential of redox tags for organic synthesis.
含氧分子在自然和人工环境中无处不在，使得 present C-O 键的氧化还原转化成为处理这些分子的核心工具。然而，传统上所需的（超）化学计量氧化还原试剂包括高度反应性和危险的试剂，这带来了多个实际挑战，包括过程安全危害或特殊废物管理要求。在这里，我们报告了一种温和的 Ni 催化断裂策略，该策略基于碳酸盐氧化还原标签，用于在没有任何外部氧化还原当量或其他添加剂的情况下对含氧烃进行氧化还原转化。这个纯粹的催化过程能够使强 C(sp)-O 键发生氢解，包括烯醇碳酸酯的氢解，以及在温和条件下（低至室温）使 C-O 键发生催化氧化。此外，我们研究了其潜在的反应机理，并在多个应用中展示了碳酸盐氧化还原标签的优势。更广泛地说，本文的工作证明了氧化还原标签在有机合成中的潜力。
