Visible-Light-Mediated Energy Transfer Enables Intramolecular Cyclization of O‑Acetyloximes to Phenanthridines

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 - phenanthridines

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%); R_f = 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.