Synthesis of Bridged Diketopiperazines by Using the Persistent Radical Effect and a Formal Synthesis of Bicyclomycin

A conceptually new and unified approach to diverse bridged diketopiperazines (DKPs) with widely variable ring sizes was developed by taking advantage of the persistent radical effect. This method enables synthesis of the core structures of bridged DKP alkaloids and was applied to a formal synthesis of the antibiotic bicyclomycin. Persistent cyclization: A unified radical approach to diverse bridged diketopiperazines was developed by taking advantage of the persistent radical effect. The method allows rapid access to three‐dimensional heterocyclic architectures and was applied to a formal synthesis of the antibiotic bicyclomycin.