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Cuprous(I) catalysts have been widely used in the coupling reaction of forming C‐X bond. The core‐modified porphyrins are known to stabilize the unusual oxidation state of many metals. Thus, in this work, a 21‐oxaporphyrin was obtained under the improved Adler–Longo condensation condition and successfully used for complexing the cuprous ion. It is found that the synergy of the two factors, the diameter...