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Synthesis 2025; 57(22): 3507-3520
DOI: 10.1055/a-2669-6062
Paper

A Facile Light-Driven C–S Bond Formation: Photosensitized Benzophenone Preparation of Thioethers from Alkenes

Authors

  • Hugo Sebastian Steingrüber

    1   Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Intendente Güiraldes 2160, C1428EGA Buenos Aires, Argentina
    2   Unidad de Microanálisis y Métodos Físicos aplicados a Química Orgánica (UMYMFOR), CONICET, C1428EGA Buenos Aires, Argentina

  • Adrian Daniel Hund 

    1   Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Intendente Güiraldes 2160, C1428EGA Buenos Aires, Argentina
    2   Unidad de Microanálisis y Métodos Físicos aplicados a Química Orgánica (UMYMFOR), CONICET, C1428EGA Buenos Aires, Argentina

  • Juan Bautista Rodriguez 

    1   Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Intendente Güiraldes 2160, C1428EGA Buenos Aires, Argentina
    2   Unidad de Microanálisis y Métodos Físicos aplicados a Química Orgánica (UMYMFOR), CONICET, C1428EGA Buenos Aires, Argentina

  • Sergio Hernán Szajnman

    1   Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Intendente Güiraldes 2160, C1428EGA Buenos Aires, Argentina
    2   Unidad de Microanálisis y Métodos Físicos aplicados a Química Orgánica (UMYMFOR), CONICET, C1428EGA Buenos Aires, Argentina

  • Sergio Bonesi

    1   Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Intendente Güiraldes 2160, C1428EGA Buenos Aires, Argentina
    3   Centro de Investigaciones en Hidratos de Carbono (CIHIDECAR), CONICET, C1428EGA Buenos Aires, Argentina

S.M.B. is grateful to Universidad de Buenos Aires for Grant 20020190100242BA and to Consejo Nacional de Investigaciones Científicas y Técnicas for Grant PIP 112-02001-00585CO. J.B.R. is grateful to Universidad de Buenos Aires for Grant 20020220200020BA; to Consejo Nacional de Investigaciones Científicas y Técnicas for Grant PIP 112-202001-01544CO and Agencia Nacional de Promoción Científica y Tecnológica for Grant PICT2021-I-A-00887.
Gefördert durch: Agencia Nacional de Promoción Científica y Tecnológicas PICT2021-I-A-00887
Gefördert durch: Consejo Nacional de Investigaciones Científica y Técnicas PIP 112-02001-00585CO,PIP 112-202001-01544CO
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Abstract

A simple, metal- and oxidant-free photosensitized reaction has been developed to promote the hydrothiolation of olefins using benzophenone as an inexpensive photocatalyst at room temperature. The photoinduced reaction involves an anti-Markovnikov addition of a wide variety of alkyl thiols and thiophenol to an interesting family of activated and, particularly, inactivated alkenes, which are formed in good to excellent yields and with high regioselectivity. The present photosensitized reaction is operationally simple, tolerates a variety of functional groups, and proceeds efficiently within 1 h of reaction time. Additional experiments were also carried out to shed some light on the reaction mechanism. The course of the photoreaction was followed by 1H NMR spectroscopy and was quenched with 2,2,6,6-tetramethylpiperidyl-1-oxyl (TEMPO), known for efficient radical trapping, demonstrating that a radical chain process is involved, and the use of deuterated solvents showed a primary isotope effect. The on–off mechanistic experiment was also carried out demonstrating that light is a required reagent and the radical intermediate of the photoreaction is quickly quenched when the light is off. Based on these results, a plausible reaction mechanism was proposed.

Keywords

Photosensitization - Hydrothiolation reaction - Thioethers - Anti-Markovnikov selectivity - Reaction mechanism

Supplementary Material



Publikationsverlauf

Eingereicht: 19. Juni 2025

Angenommen nach Revision: 28. Juli 2025

Accepted Manuscript online:
29. Juli 2025

Artikel online veröffentlicht:
25. August 2025

© 2025. Thieme. All rights reserved.

Georg Thieme Verlag KG
Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany

 

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