20.500.12556/RUL-180117 Amine-cation-driven heteroannulation of halomaleimides with C–N cleavage metal-free access to heterobicyclic frameworks Maleimides 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. heterobicyclic and 3 4-diamino-substituted maleimides halomaleimides C-N cleavage quaternary enamine intermediate mechanistic studies metal-free mild conditions heterocycles heterobiciklični in 3 4-diamino-substituirani maleimidi halomaleimidi cepitev vezi C-N kvaternarni enaminski intermediati mehanistične študije blagi pogoji brez kovin heterocikli true false true Angleški jezik Slovenski jezik Članek v reviji 2026-03-03 10:31:59 2026-03-03 10:32:01 2026-05-15 04:46:11 0000-00-00 00:00:00 2026 0 0 Str. 2114-2121 iss. 7 Vol. 13 31 Mar. 2026 0000-00-00 Zaloznikova Objavljeno NiDoloceno 0000-00-00 0000-00-00 0000-00-00 547.7 2052-4129 10.1039/D6QO00010J 268833795 RAZ_Ciber_Luka_2026.pdf RAZ_Ciber_Luka_2026.pdf 1 E7553DC9C01C8B3E96B12D9813FE0F30 685757a5b0ef2be01ff199e2c33b75f9b84bc57f5ad589f516da28e830916618 eefae37a-4f81-11f1-b0ab-0050569b8976 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=233854 https://pubs.rsc.org/en/content/articlelanding/2026/qo/d6qo00010j 1 7ec3528c-16e3-11f1-a1ba-0050569b8976 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=229224 Fakulteta za kemijo in kemijsko tehnologijo 0 0 0