Efficient Three‐Component Cyanation Synthesis of Quinoline Under Solvent‐Free and Additive‐Free Conditions

ABSTRACT An efficient dearomative cyanidation of quinoline is described, which enables the synthesis of a series of α‐cyanoquinolines under solvent‐free and additive‐free conditions (29 examples, yield up to 99%). By using low‐toxicity and commercially available starting materials, this method allows for direct α‐position cyanation, exhibiting broad functional group compatibility and excellent scalability for gram‐scale (10 mmol, 97% yield) synthesis with consistently high yields. Furthermore, the different reaction pathways that lead to the experimentally observed products were investigated through DFT calculations and NMR studies.