| Autor: |
Giuseppe Zuccarello, Leonardo J. Nannini, Ana Arroyo-Bondía, Nicolás Fincias, Isabel Arranz, Alba H. Pérez-Jimeno, Matthias Peeters, Inmaculada Martín-Torres, Anna Sadurní, Víctor García-Vázquez, Yufei Wang, Mariia S. Kirillova, Marc Montesinos-Magraner, Ulysse Caniparoli, Gonzalo D. Núñez, Feliu Maseras, Maria Besora, Imma Escofet, Antonio M. Echavarren |
| Rok vydání: |
2023 |
| DOI: |
10.26434/chemrxiv-2023-vxlcf |
| Popis: |
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 a dialkylphenyl phosphine. The new chiral gold(I) cata-lysts 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 a dialkylphenyl phosphine led to the formation of the opposite enantiomers. The chiral binding pockets of the new catalysts have been analyzed by DFT calcula-tions. As revealed by NCI plots, attractive non-covalent interactions between substrates and catalysts direct the specific enantiose-lective 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. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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