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Updated: Apr 6, 2026

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Double-Stereodifferentiation in Rhodium-Catalyzed [2 + 2 + 2] Cycloaddition: Chiral Ligand/Chiral Counterion Matched
Mylène Augé1, Alexandra Feraldi-Xypolia1, Marion Barbazanges1
1†Sorbonne Universités, UPMC Univ Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu, Paris 75252 Cedex 05, France.
Abstract:
The first enantioselective metal-catalyzed [2 + 2 + 2] cycloaddition involving a double asymmetric induction has been devised. It relies on the use of an in situ generated chiral cationic rhodium(I) catalyst with a matched chiral ligand/chiral counterion pair. Careful optimization of the catalytic system, as well as of the reaction conditions, led to atroposelective [2 + 2 + 2] pyridone cycloadducts with high ee's up to 96%. This strategy outperformed those previously described involving a chiral ligand only or a chiral counterion only.
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