Photochemical rearrangement of diarylethenes: synthesis of functionalized phenanthrenes

A novel protocol for the synthesis of functionalized phenanthrenes through photocyclization of diarylethenes (DAE) under UV irradiation is proposed. The reaction proceeds through 6π-electrocyclization with the formation of a cyclic (closed) intermediate that undergoes a rearrangement affording unsym...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2020-04, Vol.18 (16), p.398-313
Main Authors: Zakharov, A. V, Yadykov, A. V, Lvov, A. G, Mitina, E. A, Shirinian, V. Z
Format: Article
Language:English
Subjects:
Aromatic compounds
Benzene
Crystallography
Imidazole
Irradiation
Mass spectra
Naphthalene
NMR
Nuclear magnetic resonance
Oxazole
Photochemicals
Pyrazole
Ultraviolet radiation
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Summary:A novel protocol for the synthesis of functionalized phenanthrenes through photocyclization of diarylethenes (DAE) under UV irradiation is proposed. The reaction proceeds through 6π-electrocyclization with the formation of a cyclic (closed) intermediate that undergoes a rearrangement affording unsymmetrical phenanthrenes in good yields. However, in contrast to benzene derivatives, the photocyclization of naphthalene diarylethenes proceeds more slowly, which is confirmed by DFT calculations. The transformation was performed on a 1 mmol scale. The scalability showed that the diarylethenes bearing oxazole, thiazole, pyrazole and imidazole as aryl moieties are more prone to photorearrangement and can be used in preparative organic synthesis. The photocyclization of diarylethenes bearing naphthalene units was explored and a convenient protocol for the synthesis of functionalized phenanthrenes was proposed.
ISSN:1477-0520
1477-0539
DOI:10.1039/d0ob00296h