瑞士巴塞尔大学Sparr Christof团队报道了芳香环开环复分解。相关研究成果于2024年12月11日发表在《自然》。

芳香族化合物因其稳定性、特征性相互作用、确定的分子形状，以及通过多种环化反应合成的多种合成方法，而在化学和材料科学中得到广泛应用。相比之下，由于在开环时破坏芳香性的不利能量，惰性芳香碳-碳键的裂解在很大程度上仍然不可行。

对于非芳香结构，过渡金属亚烷基催化的烯烃复分解，被确定为最通用的碳-碳键形成和断裂反应之一。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实现。

该文中，研究人员报道了使用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，芳香环开环复分解（ArROM）反应。每种环系统的反应都是通过独特的亚烷基中间体进行的。

研究人员进一步证明了，通过精细的催化剂控制阻转异构体的构型，进行立体选择性芳香环开环复分解的可能性。因此，芳香环开环复分解是一种可行且有效的方法，可以在不需要任何试剂或光激发的情况下，催化转化和相互转化各种芳香族化合物。

附：英文原文

Title: Aromatic ring-opening metathesis

Author: Hutskalova, Valeriia, Sparr, Christof

Issue&Volume: 2024-12-11

Abstract: 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 reactions2,3. 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.

DOI: 10.1038/s41586-024-08472-z

Source: https://www.nature.com/articles/s41586-024-08472-z