Pd-catalyzed methylene γ-C(sp3)—H alkenylation of N-picolinoylcycloalkylamines with alkenyl iodides promoted by 2-tert-butyl-1,4-benzoquinone

[Display omitted] A palladium(II) acetate-catalyzed alkenylation of the methylene sp3 γ-carbon-hydrogen bonds of N-picolinoylcycloalkylamines with alkenyl iodides in the presence of silver carbonate was promoted by 2-tert-butyl-1,4-benzoquinone (TBBQ). This functionalization of N-picolinoylcyclohexy...

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Bibliographic Details
Published in:Tetrahedron letters 2021-06, Vol.74, p.153130, Article 153130
Main Authors: Seki, Atsushi, Takahashi, Yoshiaki
Format: Article
Language:English
Subjects:
Alkenylation
Carbon-hydrogen bond activation
Palladium catalysis
γ-Alkenylcycloalkylamine
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Summary:[Display omitted] A palladium(II) acetate-catalyzed alkenylation of the methylene sp3 γ-carbon-hydrogen bonds of N-picolinoylcycloalkylamines with alkenyl iodides in the presence of silver carbonate was promoted by 2-tert-butyl-1,4-benzoquinone (TBBQ). This functionalization of N-picolinoylcyclohexylamine with alkenyl iodides exclusively provided a range of cis-3-(1-alkenyl)-N-picolinoylcyclohexylamines in up to 82% yield. In contrast, the TBBQ-promoted alkenylation of a macrocyclic substrate, N-picolinoylcyclododecylamine, gave only trans-3-(1-alkenyl)-N-picolinoylcyclododecylamine as a monoalkenylation-product in up to 52% yield. Interestingly, the stereoselectivity of the product was reversed due to the increased ring size of the substrate. This is the first example of trans-γ-CH alkenylation.
ISSN:0040-4039
1873-3581
DOI:10.1016/j.tetlet.2021.153130