Dual Cu/Ir Catalyzed Asymmetric Allylation and Pictet‐Spengler Cyclization: Stereodivergent Access to Chiral Indole Fused 9‐Azabicyclo[4.2.1]nonanes†

Comprehensive Summary Nitrogen‐containing bridged‐heterocycles and indoles are key subunits of many natural products and pharmacologically active molecules. We herein present a bimetallic Cu/Ir catalyzed asymmetric allylation of ketimine esters and ( E )‐4‐indolyl allyl carbonates followed by acid‐promoted Pictet‐Spengler cyclization sequences, enabling stereodivergent synthesis of chiral indole fused 9‐azabicyclo[4.2.1]nonanes containing an eight‐membered ring with one tertiary and two quaternary stereogenic centers. This one‐pot sequential protocol features step economy, good substrate tolerance, and excellent stereoselective control.