Mechanism-Driven Development of N‑(Quinolin-8-yl)-benzamide Coupling Reactions via C–H
or N–H Activation
Posted on 2023-04-20 - 12:41
The mechanistic details of the oxidative
coupling of compounds
with a number of different redox centers are investigated using N-(quinolin-8-yl)-benzamide (L) as a model substrate. The
control of the chemical or electrooxidation parameters in the absence
or presence of a cobalt catalyst makes it possible to obtain regioselectively
different oxidative coupling products (ortho- vs para-C–H/C–H vs C–H/N–H vs N–H/N–H).
The results indicate that the operative mechanism depends on the type
of oxidized reaction center and the oxidant nature. Oxidation affects
the para-C–H bond in quinoline or the N–H
fragment or the ortho-C–H bond in the benzene
substituent in the molecule. The intermediate Co(II)[L–H]2 complex and C–H-activated CoIII metallacycle
with benzamide ligands, which are shown to oxidize at close potentials,
have been isolated and characterized by various techniques, including
X-ray diffraction and voltammetry. The strength of the oxidizing agent
affects the formation of a particular product, though not acting as
the determining factor. Two-electron oxidation of Co(II)[L–H]2 yields to C–N coupling, but one-electron oxidation
of Co(III) leads to ortho-C–C coupling. All
electrochemical reactions are performed under mild conditions at room
temperature without adding special reagents (oxidants, halides, phosphines,
etc.).
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Dolengovski, Egor L.; Gryaznova, Tatyana V.; Dudkina, Yulia B.; Islamov, Daut R.; Fayzullin, Robert R.; Sinyashin, Oleg G.; et al. (2023). Mechanism-Driven Development of N‑(Quinolin-8-yl)-benzamide Coupling Reactions via C–H
or N–H Activation. ACS Publications. Collection. https://doi.org/10.1021/acs.organomet.2c00654