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Merging Double Hydrogen Atom Transfer and Stepwise Proton-Coupled Electron Transfer for γ‑C-H Hydrazination of
Kaiming Zuo1, Phong Dam1, Kosala N Amarasinghe1
1Leibniz Institute for Catalysis e.V., Albert-Einstein-Str. 29a, Rostock 18059, Germany.
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A cobalt-(salen)-catalyzed γ-C-H hydrazination of alcohols is unveiled, merging a double hydrogen atom transfer (HAT) and a proton-coupled electron transfer (PCET) within a single catalytic cycle. The transformation harnesses metal-hydrogen atom transfer-induced radical translocation and electrophilic azodicarboxylate coupling to achieve remote C-H functionalization under mild and sustainable conditions. Mechanistic investigations (EPR, UV-vis, and spin-trapping) reveal cobalt oxidation state modulation and transient radical intermediates, while DFT analysis elucidates the double HAT/PCET pathway and site selectivity. This strategy offers an efficient and sustainable route from simple alcohols to γ-hydrazino and γ-amino alcohols.
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