This work demonstrates a new protocol for 1,2-diamination in aryl-substituted 1,3-dienes, suggesting a novel approach for controlling chemical reactivity.
Axial PPh₃ coordination enables the regioselective 1,2-diamination of aryl-substituted 1,3-dienes using dirhodium catalysis, employing N-fluorobenzenesulfonimide as the oxidant and nitrogen source. This base-free protocol proceeds via a PPh₃-stabilized dirhodium(II,III) species, facilitating efficient nitrogen radical transfer via the trans effect. The method features broad functional group tolerance (35 examples, up to 91% yield) and gram-scale scalability. This work highlights the potential of axial electronic tuning as a general strategy for controlling reactivity in a dirhodium-catalyzed radical reaction.
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Zhang et al. (2026) studied this question.
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