Nair, Akshay M.Malga Díaz, José ManuelMartínez Acevedo, NicolásFañanás-Mastral, Martín2026-04-202026-04-202026-01-28Nair, A. M., Malga, J. M., Martínez‐Acevedo, N., & Fañanás‐Mastral, M. (2026). Accessing Molecular Complexity from Methane and Other Gaseous Alkanes via Photocatalytic Cascade Cyclization. Angewandte Chemie International Edition, 65(5), e25713. https://doi.org/10.1002/anie.2025257131433-7851https://hdl.handle.net/10347/46799The direct transformation of simple and abun-dant feedstocks into structurally complex moleculesremains a central challenge in modern organic synthesis.Herein, we report a method for the oxidative cascadecyclization of N-aryl and N-benzoyl acrylamide deriva-tives, promoted by methane and other gaseous alkanes.This transformation is enabled by a readily available ironcatalyst in combination with N-fluorobenzenesulfonimide(NFSI) as the oxidant, proceeding under mild conditionsto afford a diverse array of N-heterocyclic frameworks inhigh yields. Late-stage functionalization studies highlightthe utility of methane in the synthesis of biologicallyrelevant scaffolds. Moreover, the Fe/NFSI system facili-tates a radical sampling regime that enables the selectivefunctionalization of less reactive primary C─H bonds.Overall, this work establishes a sustainable and versatileplatform for constructing molecular complexity directlyfrom gaseous alkanes.eng©2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercialNoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/2306 Química orgánicajournal article10.1002/anie.2025257131521-3773open access