Dohi Toshifumi, Elboray Elghareeb E, Kikushima Kotaro, Morimoto Koji, Kita Yasuyuki
Graduate School of Pharmaceutical Sciences, Ritsumeikan University, 1-1-1, Nojihigashi, Kusatsu Shiga 525-8577, Japan.
Research Organization of Science and Technology, Ritsumeikan University, 1-1-1, Nojihigashi, Kusatsu Shiga 525-8577, Japan.
Chem Rev. 2025 Mar 26;125(6):3440-3550. doi: 10.1021/acs.chemrev.4c00808. Epub 2025 Mar 7.
Constructing chemical bonds under green sustainable conditions has drawn attention from environmental and economic perspectives. The dissociation of (hetero)aryl-halide bonds is a crucial step of most arylations affording (hetero)arene derivatives. Herein, we summarize the (hetero)aryl halides activation enabling the direct (hetero)arylation of trapping reagents and construction of highly functionalized (hetero)arenes under benign conditions. The strategies for the activation of aryl iodides are classified into (a) hypervalent iodoarene activation followed by functionalization under thermal/photochemical conditions, (b) aryl-I bond dissociation in the presence of bases with/without organic catalysts and promoters, (c) photoinduced aryl-I bond dissociation in the presence/absence of organophotocatalysts, (d) electrochemical activation of aryl iodides by direct/indirect electrolysis mediated by organocatalysts and mediators acting as electron shuttles, and (e) electrophotochemical activation of aryl iodides mediated by redox-active organocatalysts. These activation modes result in aryl iodides exhibiting diverse reactivity as formal aryl cations/radicals/anions and aryne precursors. The coupling of these reactive intermediates with trapping reagents leads to the facile and selective formation of C-C and C-heteroatom bonds. These ecofriendly, inexpensive, and functional group-tolerant activation strategies offer green alternatives to transition metal-based catalysis.
在绿色可持续条件下构建化学键已从环境和经济角度引起关注。（杂）芳基卤化物键的断裂是大多数生成（杂）芳烃衍生物的芳基化反应的关键步骤。在此，我们总结了在温和条件下实现捕获试剂直接（杂）芳基化以及构建高度官能化（杂）芳烃的（杂）芳基卤化物活化方法。芳基碘化物的活化策略可分为：（a）高价碘芳烃活化，随后在热/光化学条件下进行官能化；（b）在有/无有机催化剂和促进剂的碱存在下芳基 - I键的断裂；（c）在有/无有机光催化剂存在下光诱导芳基 - I键的断裂；（d）通过作为电子穿梭体的有机催化剂和介质介导的直接/间接电解对芳基碘化物进行电化学活化；以及（e）由氧化还原活性有机催化剂介导的芳基碘化物的光电化学活化。这些活化模式使芳基碘化物作为形式上的芳基阳离子/自由基/阴离子和芳炔前体表现出多样的反应性。这些反应中间体与捕获试剂的偶联导致C - C键和C - 杂原子键的 facile和选择性形成。这些生态友好、廉价且官能团耐受性强的活化策略为基于过渡金属的催化提供了绿色替代方案。
