An efficient three step synthesis towards 3-amino-1,4-benzodiazepin-2-one derivatives is presented. The versatile Ugi-4-component reaction (Ugi-4CR) and Boc-deprotection is followed by a ligand-free Ullmann condensation. This protocol allows the rapid construction of a diverse array of substituted 1,5-benzodiazepinones. Since Ugi-based products are typically limited by their ‘inert’ C-terminal amides, the use of a convertible (‘cleavable’) isocyanide was envisaged and resulted in building blocks that can be made SPPS-compatible. To demonstrate the potential of this novel synthetic route, the design and preparation of novel phenylurea-1,5-bezondiazepin-4(5H)-one dipeptide mimetics with potential CCK2-antagonist properties is reported.
