Takahashi Ikko, Tortajada Andreu, Anderson David E, Ilies Laurean, Hevia Eva, Asako Sobi
RIKEN Center for Sustainable Resource Science, Wako, Japan.
Department für Chemie, Biochemie und Pharmacie, Universität Bern, Bern, Switzerland.
Nat Synth. 2025;4(7):816-825. doi: 10.1038/s44160-025-00771-1. Epub 2025 Mar 25.
Sodium is one of the most abundant elements on Earth and a sustainable alternative to less sustainable metals such as lithium, which is becoming increasingly depleted and expensive. Traditionally, however, organosodium reagents have been considered highly reactive, engaging in uncontrollable reactions, and as a result, they have been scarcely used in organic synthesis, especially in combination with transition-metal catalysis. Here we report the use of organosodium compounds as C( )-Na nucleophilic partners in iron-catalysed oxidative homocoupling and cross-coupling with alkyl halides. Mechanistic investigations based on the preparation and characterization of putative organoiron intermediates reveal that a bidentate additive coordinates both sodium and the iron centre, exerting control over the catalytic reactivity. This combination of two abundant and non-toxic metals, powered by molecular-level mechanistic understanding, is expected to open new avenues for the use of sustainable organometallic reagents in organic synthesis.
钠是地球上含量最丰富的元素之一，是锂等可持续性较差的金属的一种可持续替代物，锂正变得日益枯竭且昂贵。然而，传统上有机钠试剂被认为具有高反应活性，会发生不可控反应，因此，它们在有机合成中很少被使用，尤其是与过渡金属催化结合使用时。在此，我们报道了在铁催化的氧化均偶联以及与卤代烃的交叉偶联反应中，使用有机钠化合物作为C（ ）-Na亲核试剂。基于假定的有机铁中间体的制备和表征所进行的机理研究表明，一种双齿添加剂能同时配位钠和铁中心，从而控制催化反应活性。在分子水平机理认识的推动下，这两种丰富且无毒的金属的结合，有望为在有机合成中使用可持续有机金属试剂开辟新途径。
