Resumen: The development of chiral zeolitic catalysts possessing extra-large pores and endowed with the capability of enantioselectively processing bulky products represents one of the greatest challenges in chemistry. Here, we report the discovery of GTM-3, an enantio-enriched extra-large pore chiral zeolite material with -ITV framework structure, obtained using a simple enantiopure organic cation derived from the chiral pool, N,N-ethyl-methyl-pseudoephedrinium, as the chiral-inductor agent. We demonstrate the enantio-enrichment of GTM-3 in one of the two enantiomorphic polymorphs using the two enantiomers of the organic cation. Interestingly, we prove the ability of this zeolitic material to perform enantioselective catalytic operations with very large substrates, here exemplified by the catalytic epoxide aperture of the bulky trans-stilbene oxide with alcohols, yielding unprecedented product enantiomeric excesses up to 30%. Our discovery opens the way for the use of accessible chiral zeolitic materials for the catalytic asymmetric synthesis of chiral pharmaceutical compounds. Idioma: Inglés DOI: 10.1021/jacs.2c01874 Año: 2022 Publicado en: Journal of the American Chemical Society 144, 18 (2022), 8249-8256 ISSN: 0002-7863 Factor impacto JCR: 15.0 (2022) Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 17 / 178 = 0.096 (2022) - Q1 - T1 Factor impacto CITESCORE: 25.7 - Biochemistry, Genetics and Molecular Biology (Q1) - Chemistry (Q1) - Chemical Engineering (Q1)