Highly Substituted 1,4‐Benzodiazepin‐2‐ones: A Rapid Modular Approach From Arynes and Unsymmetrical Imides

We present a method for the rapid assembly of highly substituted 1,4‐benzodiazepin‐2‐ones by the addition of unsymmetrical imides to arynes, the subsequent deprotection of a protected amino functionality followed by immediate ring closure. An optimized procedure for the synthesis of diversely substituted unsymmetrical imides was developed, granting access to a large pallet of benzodiazepine precursors. This allows for the application of this protocol in a modular fashion, which is demonstrated for both the unsymmetrical imides and the benzodiazepines. Ultimately, we thereby reveal rapid access to a large variety of densely functionalized benzodiazepine cores.