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A new mode of reactivity of 1,3‐diynes in rhodium‐catalyzed oxidative annulation reactions has enabled the rapid assembly of extended π systems from readily available picolinamide derivatives. The process involves a double C−H bond activation and the iterative annulation of two 1,3‐diyne units, with each alkyne moiety engaged in an orchestrated insertion sequence with high regiocontrol, leading to...
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