Gold-Catalyzed Migratory Insertion of Alkynes

Migratory insertion is a key elementary step within organometallic chemistry, frequently encountered with most transition metals. However, in the realm of gold catalysis, the migratory insertion step has remained elusive for a long time. Herein, we disclose the migratory insertion of alkynes into Au­(III)–C bonds in a catalytic fashion. Experimental results suggest that the migratory insertion pathway predominates over the π-activation pathway, a finding further supported by the Density Functional Theory (DFT) calculations. The observed regioselectivity underscores the distinct advantages and complementarity of gold catalysis in comparison with palladium catalysis. Furthermore, the utility of the protocol has been demonstrated for the synthesis of various Polycyclic Aromatic Hydrocarbons (PAHs) via Scholl’s reaction.迁移插入（migratory insertion）是有机金属化学中的关键基元步骤，多数过渡金属参与的反应中均频繁涉及该过程。然而长期以来，金催化领域中的迁移插入步骤始终难以捉摸。本文首次报道了催化模式下炔烃向三价金-碳键中的迁移插入反应。实验结果表明，迁移插入路径相较于π活化路径占据主导地位，这一结论进一步得到了密度泛函理论（Density Functional Theory，DFT）计算的支持。所观察到的区域选择性凸显了金催化相较于钯催化的独特优势与互补性。此外，本催化方法的实用性已通过经由肖尔（Scholl）反应合成各类多环芳烃（Polycyclic Aromatic Hydrocarbons，PAHs）的实例得到验证。