Conventional chiral ligands rely on the use of a covalently constructed, single chiral molecule embedded with coordinative functional groups. Here, we report a new strategy for the design of a chiral ligand for asymmetric transition-metal catalysis; our approach is based on the development of an achiral cationic ammonium–phosphine hybrid ligand paired with a chiral binaphtholate anion. This ion-paired chiral ligand imparts a remarkable stereocontrolling ability to its palladium complex, which catalyses a highly enantioselective allylic alkylation of α-nitrocarboxylates. By exploiting the possible combinations of the achiral onium entities with suitable coordinative functionalities and readily available chiral acids, this approach should contribute to the development of a broad range of metal-catalysed, stereoselective chemical transformations.
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Financial support was provided by the Funding Program for Next Generation World-Leading Researchers from JSPS (GR050) and the Global COE Program in Chemistry of Nagoya University.
The authors declare no competing financial interests.
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Ohmatsu, K., Ito, M., Kunieda, T. et al. Ion-paired chiral ligands for asymmetric palladium catalysis. Nature Chem 4, 473–477 (2012). https://doi.org/10.1038/nchem.1311
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