Abstract
Asymmetric photocatalysis has emerged as a powerful strategy for constructing chiral molecules under mild conditions, yet the enantioselective activation of aromatic enol systems via visible light remains a significant challenge. In particular, the photochemical dearomatization of salicyclaldehydes through excited-state intramolecular proton transfer (ESIPT) offers unique reactivity but has rarely been harnessed in catalytic asymmetric synthesis. Herein, we report an asymmetric de Mayo reaction catalyzed by a chiral hafnium phosphate complex, enabling visible-light-promoted dearomatization and exo-aromatic C–C bond insertion of salicylaldehyde derivatives with alkenes. By leveraging the unique photophysical properties of ESIPT systems, we demonstrate that coordination of 1-hydroxy-2-naphthaldehyde to a Hf(IV)–chiral phosphate catalyst induces a significant red-shift in absorption, activating the substrate under 480 nm irradiation. This strategy not only enhances photochemical reactivity but also provides excellent stereocontrol, yielding insertion products in up to 95% yield and 98% ee. Mechanistic studies, including transient spectroscopy and DFT calculations, reveal that the reaction proceeds via a triplet-state [2 + 2] cycloaddition pathway facilitated by hafnium-centered ligand-to-metal charge transfer (LMCT). This work establishes a distinctive catalytic strategy for enantioselective transformations of aromatic enol systems under visible light and expands the synthetic utility of ESIPT-driven photochemistry.
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Acknowledgements
We thank the High Performance Computing Center, Tsinghua University, for their kind supporting, as long as all people who had ever provided help or advice to this work. Funding: This work is supported by the Fundamental and Interdisciplinary Disciplines Breakthrough Plan of the Ministry of Education of China (JYB2025XDXM414), Natural Science Foundation of China (22031006; 22373056 and 22393891), the National Key R&D Program of China (2023YFA1506401; 2023YFA1506402), the robotic AI-Scientist platform of the Chinese Academy of Sciences and Haihe Laboratory of Sustainable Chemical Transformations for financial support.
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Yang, C., Wang, Y., Zhang, Y. et al. Chiral hafnium phosphate catalyzed asymmetric de Mayo reaction via visible-light-induced dearomatization. Nat Commun (2026). https://doi.org/10.1038/s41467-026-72827-5
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DOI: https://doi.org/10.1038/s41467-026-72827-5
