Light-enabled deracemization of cyclopropanes by Al-salen photocatalysis

Carina Onneken, Tobias Morack, Julia Soika, Olga Sokolova, Niklas Niemeyer, Christian Mück-Lichtenfeld, Constantin G. Daniliuc, Johannes Neugebauer () and Ryan Gilmour ()
Additional contact information
Carina Onneken: Westfälische Wilhelms-Universität (WWU) Münster
Tobias Morack: Westfälische Wilhelms-Universität (WWU) Münster
Julia Soika: Westfälische Wilhelms-Universität (WWU) Münster
Olga Sokolova: Westfälische Wilhelms-Universität (WWU) Münster
Niklas Niemeyer: Westfälische Wilhelms-Universität (WWU) Münster
Christian Mück-Lichtenfeld: Westfälische Wilhelms-Universität (WWU) Münster
Constantin G. Daniliuc: Westfälische Wilhelms-Universität (WWU) Münster
Johannes Neugebauer: Westfälische Wilhelms-Universität (WWU) Münster
Ryan Gilmour: Westfälische Wilhelms-Universität (WWU) Münster

Nature, 2023, vol. 621, issue 7980, 753-759

Abstract: Abstract Privileged chiral catalysts—those that share common structural features and are enantioselective across a range of reactions—continue to transform the chemical-research landscape1. In recent years, new reactivity modes have been achieved through excited-state catalysis, processes activated by light, but it is unclear if the selectivity of ground-state privileged catalysts can be matched. Although the interception of photogenerated intermediates by ground-state cycles has partially addressed this challenge2, single, chiral photocatalysts that simultaneously regulate reactivity and selectivity are conspicuously scarce3. So far, precision donor–acceptor recognition motifs remain crucial in enantioselective photocatalyst design4. Here we show that chiral Al-salen complexes, which have well-defined photophysical properties, can be used for the efficient photochemical deracemization5 of cyclopropyl ketones (up to 98:2 enantiomeric ratio (e.r.)). Irradiation at λ = 400 nm (violet light) augments the reactivity of the commercial catalyst to enable reactivity and enantioselectivity to be regulated simultaneously. This circumvents the need for tailored catalyst–substrate recognition motifs. It is predicted that this study will stimulate a re-evaluation of many venerable (ground-state) chiral catalysts in excited-state processes, ultimately leading to the identification of candidates that may be considered ‘privileged’ in both reactivity models.

Date: 2023
References: Add references at CitEc
Citations: View citations in EconPapers (1)

Downloads: (external link)
https://www.nature.com/articles/s41586-023-06407-8 Abstract (text/html)
Access to the full text of the articles in this series is restricted.

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:nature:v:621:y:2023:i:7980:d:10.1038_s41586-023-06407-8

Ordering information: This journal article can be ordered from
https://www.nature.com/

DOI: 10.1038/s41586-023-06407-8

Access Statistics for this article

Nature is currently edited by Magdalena Skipper

More articles in Nature from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().