德国雷根斯堡大学Knig, Burkhard报道了能够自适应动态均相催化反应的通用交叉偶联。相关研究成果发表在2023年6月14日出版的国际学术期刊《自然》。

交叉偶联反应是现代有机合成中最重要的转化之一。尽管考虑到各种方案，已报道的（het）芳基卤化物和亲核试剂偶联伴侣的范围非常大，但不同化合物类别之间的反应条件差异很大，因此需要重新对反应条件进行逐案优化。

该文中，研究人员介绍了在可见光驱动的氧化还原反应条件下，镍的自适应动态均相催化（AD HoC）用于一般的C(sp2)-（杂）原子偶联反应。催化体系的自调节性质能够在交叉偶联反应中对数十种不同类别的亲核试剂进行简单分类。这在九种不同的成键反应中得到了综合证明（在这种情况下，C（sp2）-S、Se、N、P、B、O、C（sp3、sp2、sp）、Si、Cl），在可预测的反应条件下有数百个合成实例。催化反应中心和条件因添加的亲核试剂或（如果需要）市售的廉价胺碱而彼此不同。

附：英文原文

Title: General cross-coupling reactions with adaptive dynamic homogeneous catalysis

Author: Ghosh, Indrajit, Shlapakov, Nikita, Karl, Tobias A., Dker, Jonas, Nikitin, Maksim, Burykina, Julia V., Ananikov, Valentine P., Knig, Burkhard

Issue&Volume: 2023-06-14

Abstract: Cross-coupling reactions are among the most important transformations in modern organic synthesis1,2,3. Although the range of reported (het)aryl halides and nucleophile coupling partners is very large considering various protocols, the reaction conditions vary considerably between compound classes, necessitating renewed case-by-case optimization of the reaction conditions4. Here we introduce adaptive dynamic homogeneous catalysis (AD-HoC) with nickel under visible-light-driven redox reaction conditions for general C(sp2)–(hetero)atom coupling reactions. The self-adjustive nature of the catalytic system allowed the simple classification of dozens of various classes of nucleophiles in cross-coupling reactions. This is synthetically demonstrated in nine different bond-forming reactions (in this case, C(sp2)–S, Se, N, P, B, O, C(sp3,sp2,sp), Si, Cl) with hundreds of synthetic examples under predictable reaction conditions. The catalytic reaction centre(s) and conditions differ from one another by the added nucleophile, or if required, a commercially available inexpensive amine base.

DOI: 10.1038/s41586-023-06087-4

Source: https://www.nature.com/articles/s41586-023-06087-4