Amine-cation-driven heteroannulation of halomaleimides with C–N cleavageCiber, Luka (Avtor) Brodnik, Helena (Avtor) Petek, Nejc (Avtor) Svete, Jurij (Avtor) Grošelj, Uroš (Avtor) Štefane, Bogdan (Avtor) heterobicyclic and 34-diamino-substituted maleimideshalomaleimidesC-N cleavagequaternary enamine intermediatemechanistic studiesmetal-free mild conditionsheterocyclesMaleimides and their derivatives are highly versatile scaffolds with broad applications in synthetic chemistry, medicinal chemistry, and materials science; however, methods to expand their structural diversity remain limited. Here, we present a so far undescribed, metal-free, and mild strategy for the rapid construction of functionalized maleimides from readily available dihalomaleimide derivatives. The reaction is initiated by tertiary amine-mediated formation of an ammonium cation, which directs heteroannulation to efficiently generate heterobicyclic scaffolds. This modular approach also enables the synthesis of 3,4-diamino-substituted maleimides, including challenging second halogen substitutions with weak nucleophiles. Mechanistic studies indicate that a quaternary enamine intermediate plays a central role in steering the transformation, providing broad functional group tolerance and synthetically useful yields. Overall, this strategy offers a versatile platform for accessing structurally diverse maleimides, unlocking new opportunities in bioconjugation, medicinal chemistry, and materials science.20262026-03-03 10:31:59Članek v reviji180117UDK: 547.7ISSN pri članku: 2052-4129DOI: 10.1039/D6QO00010JCOBISS_ID: 268833795sl