Ramírez López, PedroRomero-Arenas, AntonioIglesias-Sigüenza, JavierFernández, RosarioRos, AbelLassaletta, José María2025-07-292025-07-292024Romero‐Arenas A, Ramírez‐López P, Iglesias‐Sigüenza J, Fernández R, Ros A, Lassaletta JM. Axially Chiral N ‐Oxide Catalysts for the Allylation and Crotylation of Aromatic Aldehydes: Exploiting Nonlinear Effects. ChemCatChem 2024;16:e202400806. https://doi.org/10.1002/cctc.202400806.10.1002/cctc.202400806https://hdl.handle.net/20.500.14352/122845We thank the Spanish MICINN (grants PID2019–106358GB- C21, PID2019–106358GB-C22, PID2022–137888NB-I00, PID-143230NB-I00; European FEDER funds and the Junta de Andaluciá (Grants P18-FR-3531, P18-FR-644, US-1262867) for financial support.A new family of IAN-type amine N-oxides is presented as catalysts for the allylation and crotylation of aromatic aldehydes with allyltrichlorosilanes. These reactions exhibit a remarkably positive nonlinear effect which enables the utilization of the catalysts in subenantiopure form. As enantiopure catalysts are not required under this regime, the synthesis of these N-oxides is straightforward through catalytic asymmetric synthesis, avoiding lengthy synthesis from the chiral pool or resolution of diastereoisomers. Studies of the corresponding crotylation with Z- and E-crotylsilanes suggest that the reaction proceeds through a chair-like transition state.engAttribution-NonCommercial 4.0 Internationalhttp://creativecommons.org/licenses/by-nc/4.0/journal articlehttps://doi.org/10.1002/cctc.202400806open access547544.47OrganocatalysisNonlinear effectsN-oxidesAllylationTrichlorosilanesCienciasQuímicaQuímica orgánica (Química)Ciencias Biomédicas23 Química24 Ciencias de la Vida2306 Química Orgánica2210.01 Catálisis