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Direct α‑Alkenylation of Cyclic Amines with Maleimides through Fe(III)-Catalyzed C(sp3)–H/C(sp2)–H Cross Dehydrogenative Coupling

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journal contribution
posted on 06.08.2021, 10:43 authored by Fang Wang, Qianting Zhou, Xinying Zhang, Xuesen Fan
Presented herein is a novel and efficient α-C­(sp3)–H alkenylation of cyclic amines with maleimides. Mechanistically, this C­(sp3)–H/C­(sp2)–H cross dehydrogenative coupling (CDC) reaction involves a cascade procedure including oxidative α-amino radical formation from the cyclic amine substrate and nucleophilic addition of the in situ formed α-amino radical onto the electron-deficient carbon–carbon double bond of maleimide followed by oxidation and β-elimination. Notably, this direct α-functionalization provides an effective alternative to the conventional ionic reaction mode, in which an imine or iminium intermediate is formed to react with electron-rich coupling partners other than electron-deficient ones. In general, this method features readily available and structurally diverse substrates, a green and economical catalyst, a unique reaction pathway, mild reaction conditions, high efficiency, and excellent atom economy. This new reaction enriches the application of Fe­(III)-catalyzed C­(sp3)–H activation and functionalization.