Bis-Cycloruthenated Complexes in Visible Light-Induced C–H Alkylation with Epoxides
Bis-cycloruthenated complexes (BCRCs) of the type [Ru(N^C)<sub>2</sub>L<sub>2</sub>] are proposed to be key reactive intermediates in the Ru(II)-catalyzed directed C-H functionalization of arenes. While the exceptional ground state reactivity of BCRCs toward a number of electrophiles has been explored, their reactivity upon photoexcitation is still unknown. Herein, we report studies on the photoexcitation of BCRCs that establish their capability to access chemically useful excited states. Remarkably, photoexcited BCRCs demonstrate greatly increased reactivity toward the electron transfer processes required for alkyl halide activation, overcoming current limitations of their ground-state reactivity. We have demonstrated this reactivity by expanding upon the current chemical space occupied by Ru-catalyzed C-H functionalization to include <i>ortho</i>-alkylation with epoxides.
Authors
- Igor Larrosa (ORCID: https://orcid.org/0000-0002-5391-7424)
- Mishra Deepak Hareram (ORCID: https://orcid.org/0000-0001-7512-0902)
- Alexander P. Golovanov (ORCID: https://orcid.org/0000-0002-8592-3984)
- Lauren Walker (ORCID: https://orcid.org/0000-0003-2459-7860)
- Louise S. Natrajan (ORCID: https://orcid.org/0000-0002-9451-3557)
- Ignacio Pérez‐Ortega (ORCID: https://orcid.org/0000-0001-5070-7141)
- Adam W. Woodward
- Gang‐Wei Wang (ORCID: https://orcid.org/0000-0002-3779-4495)
- Cassandre C. Bories (ORCID: https://orcid.org/0000-0002-1337-7953)
- K. W. Bentley (ORCID: https://orcid.org/0000-0003-1133-3938)
- Alexander A. V. Millman (ORCID: https://orcid.org/0000-0002-0843-4722)
- Luke M. Nichols (ORCID: https://orcid.org/0000-0002-8955-8523)
Institutions
- University of Manchester (GB)
- State Key Laboratory of Applied Organic Chemistry
- Lanzhou University (CN)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-02-04
- DOI
- https://doi.org/10.1021/jacs.4c14835
- Citations
- 6
- Primary Topic
- Radical Photochemical Reactions
- Type
- article
- Field-Weighted Citation Impact
- 5.62
Funders
- Engineering and Physical Sciences Research Council
- H2020 European Research Council