Calcium‐Catalyzed Synthesis of 1,2‐Disubstituted 3‐Benzazepines

A short and highly stereoselective chiral pool synthesis of tetrahydro‐3‐benzazepines as potential drug molecules is described, using simple enantiopure amino acids as the chiral building blocks. Intramolecular Friedel–Crafts alkylation towards seven‐membered rings was achieved with high diastereoselectivity for the first time and accomplished by a biocompatible calcium catalyst. The simple and cost efficient approach allows for the variation of all substituents in the 3‐benzazepine by a change of the substitution pattern in one or more of the reagents, while leaving the general synthetic route unchanged. Furthermore, assignment of the absolute configuration of the 3‐benzazepine derivative is straightforward, based on the amino acid building block employed.