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Photochemistry of 2-acyloxycarbazoles. A potential tool in the synthesis of carbazole alkaloids

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Abstract

The photochemistry of two 2-acyloxycarbazoles, 2-acetyl- and 2-benzoyloxycarbazole, in different solvents has been studied. Irradiation of the 2-acyloxycarbazoles in organic media at 254 or 313 nm yields the [1,3]-migrated photoproducts, 1-acyl-2-hydroxycarbazole, 3-acyl-2-hydroxycarbazole and 2-hydroxycarbazole. The effects of the solvent, the atmosphere and the intensity of the light source on the photochemistry of 2-acyloxycarbazole have been studied. Laser flash photolysis as well as photosensitization experiments were performed in order to determine the photoreactive excited state. Electronic spectra (absorption, fluorescence and phosphorescence emission spectra) of the 2-acyloxycarbazoles have been recorded in homogeneous media at 298 K and in solid matrices at 77 K. The dynamic properties of the lowest singlet excited state in terms of fluorescence lifetime and fluorescence quantum yield have been measured in different organic solvents at room temperature. The photo-Fries rearrangement as a mild and clean one-pot reaction for the preparation of an advanced intermediate precursor in the total synthesis of carbazole alkaloids is described.

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Authors and Affiliations

  1. CIHIDECAR-CONICET, Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón II, 3er Piso, Ciudad Universitaria, 1428, Buenos Aires, Argentina

    Sergio M. Bonesi, Laura K. Crevatín & Rosa Erra-Balsells

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  1. Sergio M. Bonesi
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  2. Laura K. Crevatín
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  3. Rosa Erra-Balsells
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Dedicated to the memory of Prof. Adolfo R. Frasca.

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Bonesi, S.M., Crevatín, L.K. & Erra-Balsells, R. Photochemistry of 2-acyloxycarbazoles. A potential tool in the synthesis of carbazole alkaloids. Photochem Photobiol Sci 3, 381–388 (2004). https://doi.org/10.1039/b315691e

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