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oai:riubu.ubu.es:10259/105032025-05-28T00:05:25Zcom_10259_3593com_10259_5086com_10259_2604col_10259_3594

Halogen Promoted Desulfurative Cleavage of Cyclopropylmethyl Thioethers and Amination of the Formed Cyclopropylcarbinyl Cations Marín Díaz, Pablo Martínez Núñez, Clara Sanz Díez, Roberto Suárez Pantiga, Samuel Química Chemistry Química orgánica Chemistry, Organic Cyclopropylmethyl sulfides react with N-fluorosulfonimide (NFSI) or molecular iodine, enabling C−S cleavage to generate cyclopropylcarbinyl cations, which evolve through cyclopropane ring-opening reactions into homoallyl cations suitable to react with nucleophiles present in the reaction media. This desulfurative cleavage of cyclopropylmethyl thioethers under non-acidic conditions facilitates homoallylation of N-based nucleophiles such as alkyl or aryl amines as well as sulfonimides through a one-pot protocol in one or two steps depending on the nucleophile. The reaction is initiated by a halogen-sulfur bond that causes C−S bond cleavage. Moreover, the reaction with iodine proceeds through homoallyl iodide intermediates. We gratefully acknowledge Ministerio de Ciencia e Innovación (PID2020-115789GB-C21/AEI/10.13039/501100011033), and Junta de Castilla y León and FEDER (BU028P23) for financial support. C.M.-N. thanks Junta de Castilla y León for a predoctoral contract. S.S.-P. thanks a Ramón y Cajal (RYC2021-031533-I) contract funded by MCIN/AEI/10.13039/501100011033 and European Union “NextGenerationEU”/PRTR 2025-05-27T12:23:40Z 2025-05-27T12:23:40Z 2024-03 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion 1434-193X http://hdl.handle.net/10259/10503 10.1002/ejoc.202400147 1099-0690 eng European Journal of Organic Chemistry. 2024, V. 27, n. 20, p. e202400147 https://doi.org/10.1002/ejoc.202400147 Atribución-NoComercial 4.0 Internacional http://creativecommons.org/licenses/by-nc/4.0/ info:eu-repo/semantics/openAccess application/pdf Wiley