Autor segons l'article: Zuccarello, G; Nannini, LJ; Arroyo-Bondía, A; Fincias, N; Arranz, I; Pérez-Jimeno, AH; Peeters, M; Martín-Torres, I; Sadurní, A; García-Vázquez, V; Wang, YF; Kirillova, MS; Montesinos-Magraner, M; Caniparoli, U; Núñez, G; Maseras, F; Besora, M; Escofet, I; Echavarren, AM
Departament: Química Analítica i Química Orgànica
Autor/s de la URV: Arranz De La Calle, Isabel / Arroyo Bondía, Ana / Besora Bonet, Maria / Caniparoli, Ulysse Grégoire / ECHAVARREN PABLOS, ANTONIO / Martín Torres, Inmaculada / Montesinos Magraner, Marc / Nuñez, Gonzalo Darío / Pérez Jimeno, Alba Helena / Sadurní Parera, Anna / Wang, Yufei
Paraules clau: Nest tool Gold catalysis Enynes Enantioselective catalysis Dft calculations Atroposelective cyclization Asymmetric catalysis platinum pi phosphine nest tool ligands gold catalysis enynes dft calculations binol atroposelective cyclization arylalkynes allenamides alkenes 4+2 cycloadditions
Resum: A new generation of chiral gold(I) catalysts based on variations of complexes with JohnPhos-type ligands with a remote C2-symmetric 2,5-diarylpyrrolidine have been synthesized with different substitutions at the top and bottom aryl rings: from replacing the phosphine by a N-heterocyclic carbene (NHC) to increasing the steric hindrance with bis- or tris-biphenylphosphine scaffolds, or by directly attaching the C2-chiral pyrrolidine in the ortho-position of the dialkylphenyl phosphine. The new chiral gold(I) catalysts have been tested in the intramolecular [4+2] cycloaddition of arylalkynes with alkenes and in the atroposelective synthesis of 2-arylindoles. Interestingly, simpler catalysts with the C2-chiral pyrrolidine in the ortho-position of the dialkylphenyl phosphine led to the formation of opposite enantiomers. The chiral binding pockets of the new catalysts have been analyzed by DFT calculations. As revealed by non-covalent interaction plots, attractive non-covalent interactions between substrates and catalysts direct specific enantioselective folding. Furthermore, we have introduced the open-source tool NEST, specifically designed to account for steric effects in cylindrical-shaped complexes, which allows predicting experimental enantioselectivities in our systems.© 2023 The Authors. Published by American Chemical Society.
Àrees temàtiques: Physical and theoretical chemistry Organic chemistry Chemistry, multidisciplinary Chemistry (miscellaneous) Analytical chemistry
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
Adreça de correu electrònic de l'autor: anna.sadurni@urv.cat antoniomaria.echavarren@urv.cat maria.besora@urv.cat yufei.wang@estudiants.urv.cat albahelena.perez@estudiants.urv.cat inmaculada.martin@estudiants.urv.cat ulysse.caniparoli@estudiants.urv.cat ana.arroyo@estudiants.urv.cat isabel.arranz@estudiants.urv.cat
Identificador de l'autor: 0000-0002-6418-7930 0000-0002-6656-5827
Data d'alta del registre: 2024-08-03
Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
Enllaç font original: https://pubs.acs.org/doi/10.1021/jacsau.3c00159
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
Referència a l'article segons font original: Jacs Au. 3 (6): 1742-1754
Referència de l'ítem segons les normes APA: Zuccarello, G; Nannini, LJ; Arroyo-Bondía, A; Fincias, N; Arranz, I; Pérez-Jimeno, AH; Peeters, M; Martín-Torres, I; Sadurní, A; García-Vázquez, V; Wa (2023). Enantioselective Catalysis with Pyrrolidinyl Gold(I) Complexes: DFT and NEST Analysis of the Chiral Binding Pocket. Jacs Au, 3(6), 1742-1754. DOI: 10.1021/jacsau.3c00159
DOI de l'article: 10.1021/jacsau.3c00159
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2023
Tipus de publicació: Journal Publications