Tryptophan-linked dimeric diketopiperazine alkaloids possess great molecular diversity and bioactivity. In this issue of Chem, Jiang and co-workers report an oxidative approach to those alkaloids containing an unsymmetrical C3-N1′ linkage. In their concise synthesis of (+)-asperazine, they successfully dimerized a designer tryptophan-alternative building block through the sustained release of electrophilic iodine. © 2023 Elsevier Inc.