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Synlett
DOI: 10.1055/a-2550-8188
DOI: 10.1055/a-2550-8188
letter
Visible-Light-Mediated Energy Transfer Enables Intramolecular Cyclization of O‑Acetyloximes to Phenanthridines
This work was financially supported by the Natural Science Foundation of China (No. 22101070), the Natural Science Foundation of Hebei Province (Nos. B2021201015, B2023201108), the Central Government Guides Local Science and Technology Development Fund (No. 246Z1503G), and the Hebei Province Innovation Capability Enhancement Plan Project (No. 22567620H).
Abstract
O‑Acetyloximes underwent N–O bond cleavage/intramolecular cyclization under visible-light-mediated energy transfer to give phenanthridines. In contrast to the well-established approaches, no external oxidant, reductant, or additive is required for this reaction.
Key words
energy-transfer catalysis - organocatalysis - visible-light-mediated reaction - N–O bond cleavage - acetyloxime esters - phenanthridinesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2550-8188.
- Supporting Information
Publication History
Received: 12 February 2025
Accepted after revision: 04 March 2025
Accepted Manuscript online:
04 March 2025
Article published online:
09 April 2025
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- 15 Phenanthridines 2a–2af; General Procedure Two 10 mL Pyrex tubes equipped with magnetic stirrer bars were charged with the appropriate substrate 1 (0.1 mmol) and TXT (1 mol%) in toluene (3.0 mL), and the mixture in each was bubbled with a stream of argon for about 0.5 h. The samples were then irradiated by 3 W LEDs (λ = 405–410 nm) for 6 h. Upon completion of the reaction, the samples were combined, the solvent was removed under vacuum, and the residue was purified by column chromatography (silica gel, PE–EtOAc). 6-Methylphenanthridine (2a) White solid; yield: 17.0 mg (88%); Rf = 0.36 (PE–EtOAc, 3:1). 1H NMR (400 MHz, CDCl3): δ = 8.57 (d, J = 8.2 Hz, 1 H), 8.49 (d, J = 8.0 Hz, 1 H), 8.17 (d, J = 8.0 Hz, 1 H), 8.10 (d, J = 8.0 Hz, 1 H), 7.79 (t, J = 7.6 Hz, 1 H), 7.72–7.54 (m, 3 H), 3.02 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 158.9, 143.7, 132.6, 130.6, 129.4, 128.7, 127.4, 126.6, 126.4, 125.9, 123.8, 122.4, 122.0, 23.4. ESI-HRMS: m/z [M + H]+ calcd for C14H12N: 194.0964; found: 194.0964.