Enantioselective transition-metal catalysis via an anion-binding approach

John M. Ovian, Petra Vojáčková and Eric N. Jacobsen ()
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John M. Ovian: Harvard University
Petra Vojáčková: Harvard University
Eric N. Jacobsen: Harvard University

Nature, 2023, vol. 616, issue 7955, 84-89

Abstract: Abstract Asymmetric transition-metal catalysis represents a powerful strategy for accessing enantiomerically enriched molecules1–3. The classical strategy for inducing enantioselectivity with transition-metal catalysts relies on direct complexation of chiral ligands to produce a sterically constrained reactive metal site that allows formation of the major product enantiomer while effectively inhibiting the pathway to the minor enantiomer through steric repulsion4. The chiral-ligand strategy has proven applicable to a wide variety of highly enantioselective transition-metal-catalysed reactions, but important scenarios exist that impose limits to its successful adaptation. Here, we report a new approach for inducing enantioselectivity in transition-metal-catalysed reactions that relies on neutral hydrogen-bond donors (HBDs)5,6 that bind anions of cationic transition-metal complexes to achieve enantiocontrol and rate enhancement through ion pairing together with other non-covalent interactions7–9. A cooperative anion-binding effect of a chiral bis-thiourea HBD is demonstrated to lead to high enantioselectivity (up to 99% enantiomeric excess) in intramolecular ruthenium-catalysed propargylic substitution reactions10. Experimental and computational mechanistic studies show the attractive interactions between electron-deficient arene components of the HBD and the metal complex that underlie enantioinduction and the acceleration effect.

Date: 2023
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DOI: 10.1038/s41586-023-05804-3

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