Nickel-Catalyzed Coupling of Thiomethyl-Substituted 1,3-Benzothiazoles with Secondary Alkyl Grignard Reagents

Authors

  • Dr. Arash Ghaderi,

    1. Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan), Fax: (+81) 6-6879-7390
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  • Dr. Takanori Iwasaki,

    1. Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan), Fax: (+81) 6-6879-7390
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  • Asuka Fukuoka,

    1. Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan), Fax: (+81) 6-6879-7390
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  • Prof. Dr. Jun Terao,

    1. Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan)
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  • Prof. Dr. Nobuaki Kambe

    Corresponding author
    1. Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan), Fax: (+81) 6-6879-7390
    • Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan), Fax: (+81) 6-6879-7390
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Abstract

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Synthetic methods: The Ni-catalyzed alkylation of 2-(methylthio)benzothiazoles through C[BOND]S bond cleavage is reported. Reactions with various secondary alkyl nucleophiles proceeded efficiently in the presence of 1,3-butadiene as an additive. This reaction was proposed to proceed by σ-bond metathesis between the thioether and a bis(π-allyl)nickel complex or by an addition/elimination mechanism involving the C[DOUBLE BOND]N double bond of the benzothiazoles (see scheme).

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