Aromatic compounds are used across chemistry and materials science as a result of their stability, characteristic interactions, defined molecular shape and the numerous synthetic approaches for their synthesis by a diversity of cyclization reactions¹. In contrast, the cleavage of inert aromatic carbon-carbon bonds remained largely unfeasible due to the unfavourable energetics of disrupting aromaticity on ring opening. For non-aromatic structures, alkene metathesis catalysed by transition metal alkylidenes is established as one of the most versatile carbon-carbon bond-forming and breaking reactions^2,3. However, despite remarkable advancements, strategies to open aromatic compounds by metathesis remained elusive⁴. Here, we report aromatic ring-opening metathesis (ArROM) for the cleavage of aromatic rings, including tetraphene, naphthalene, indole, benzofuran and phenanthrene by employing Schrock-Hoveyda molybdenum catalysts. The reactions for each of the ring systems proceed through unique alkylidene intermediates. We further show the possibility for stereoselective aromatic ring-opening metathesis with exquisite catalyst control over the configuration of atropisomers. Aromatic ring-opening metathesis is therefore a viable and efficient approach to catalytically transform and interconvert various aromatics without the requirement for any reagents or photoexcitation.

芳香族化合物因其稳定性、特征相互作用、确定的分子形状以及通过各种环化反应合成的众多合成方法而被用于化学和材料科学¹。相比之下，惰性芳香族碳-碳键的裂解在很大程度上仍然不可行，因为在开环时破坏芳香性的能量学是不利的。对于非芳香族结构，由过渡金属烷基化合物催化的烯烃复分解被确定为最通用的碳-碳键形成和断裂反应之一^2,3。然而，尽管取得了显著进展，但通过复分解打开芳香族化合物的策略仍然难以捉摸⁴。在这里，我们报道了通过使用 Schrock-Hoveyda 钼催化剂裂解芳香环（包括四苯、萘、吲哚、苯并呋喃和菲）的芳香族开环复分解 （ArROM）。每个环系的反应都通过独特的烷基中间体进行。我们进一步展示了立体选择性芳香族开环复分解的可能性，对促异构体的构型进行了精细的催化剂控制。因此，芳香族开环复分解是一种可行且有效的方法，无需任何试剂或光激发即可催化转化和互转化各种芳烃。