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Updated: May 11, 2025

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Synthesis of 1,5-Diamino-Substituted 1,3-Dienes via Rhodium(II)-Catalyzed Tandem Reactions of
Xinran Lin1, Beiqi Yang1, Yuanhua Wang1
1College of Chemistry, Sichuan University, Chengdu 610041, China.
Abstract:
Herein, (E,E)-1,5-diamino-1,3-dienes are stereoselectively synthesized from substituted aryl derivatives via a rhodium(II)-catalyzed C(sp3)-H functionalization involving a cascade of cyclopropane ring expansion, cyclobutene formation, cyclobutene to 1,3-diene conversion, and regioselective diamination. Mechanistic studies show this one-pot process proceeds through hydrogen atom transfer (HAT), radical-polar crossover (RPC), elimination, electrocyclic ring-opening, and radical addition, underscoring rhodium(II)'s role in radical-mediated catalysis beyond traditional rhodium(II) nitrenoid chemistry.
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