北京大学焦宁团队近日实现了双齿N配体辅助过氧化氢催化金氧化还原。相关论文发表在2025年5月29日出版的《自然-化学》杂志上。

金氧化还原催化利用了强π酸活化与氧化还原反应的能力，与其他过渡金属相比，具有独特的反应活性，已成为一种有吸引力的合成方法。然而，金氧化还原化学面临着克服Au（I）/Au（III）的高氧化还原电位（1.41 V）的挑战。金氧化还原催化的经典策略采用强外部化学氧化剂，由于与官能团的不相容性，不可避免地导致原子经济性低和底物限制。

研究组报告了一种使用H₂O₂作为氧化剂的双齿N-配体（例如Phen、Bpy）辅助金氧化还原催化，该催化被证明普遍适用于多种形式的偶联反应。 此外，在该条件下，C（sp²）-C（sp²，双环化偶联）（两个环化底物的交叉偶联）是可实现的。机理研究揭示了一个氧化还原消除过程，其中双齿N-配体对催化循环至关重要。炔基AuIII-OH和乙烯基AuIII-OH物种的形成是协同π键活化和AuI氧化的关键过程。

附：英文原文

Title: Bidentate N-ligand-assisted gold redox catalysis with hydrogen peroxide

Author: Shi, Hongwei, Rudolph, Matthias, Li, Jun, Tian, Yu, Dietl, Martin C., Alshurafa, Hadil, Liu, Yaowen, Wang, Tao, Habeck, Henrik, Stein, Philipp M., Krmer, Petra, Rominger, Frank, Oeser, Thomas, Jiao, Ning, Hashmi, A. Stephen K.

Issue&Volume: 2025-05-29

Abstract: Gold redox catalysis, which exploits the ability of strong π-acid activation in combination with redox reactions, has emerged as an attractive synthetic method with unique reactivities compared to other transition metals. However, gold redox chemistry bears the challenge to overcome the high redox potential of Au(I)/Au(III) (1.41V). The classical strategy of gold redox catalysis applies strong external chemical oxidants which inevitably results in low atom economy and substrate limitations due to incompatibility with functional groups. Here we report a bidentate N-ligand (for example, Phen, Bpy) assisted gold redox catalysis using H2O2 as oxidant, which proved to be generally applicable for many forms of coupling reactions. In addition, C(sp2)–C(sp2) bicyclization coupling (cross-coupling of two cyclized substrates) is accessible under our conditions. Mechanistic studies reveal a redox elimination process in which a bidentate N-ligand is crucial for the catalytic cycle. The formation of alkynyl-AuIII–OH and vinyl-AuIII–OH species is the key process for the synergistic π-bond activation and AuI oxidation.

DOI: 10.1038/s41557-025-01835-7

Source: https://www.nature.com/articles/s41557-025-01835-7