Substituent Enabled Divergent Synthesis of N‐Heterocycles: a Metal Carbene Approach Involving Intramolecular Carbene Interception

N ‐Aryl‐ N ‐allyl‐bis‐functionalized amino‐1‐sulfonyl‐1,2,3‐trizoles undergo rhodium‐catalyzed cyclization reactions and subsequent hydrolytic cleavage of the sulfonyl imine to give two structurally distinct N ‐heterocycles, 3‐indolyl aldehydes and 3‐azabicyclo[3,1,0]hexyl aldehydes. The product ratio can be tuned by varying the electronic properties of the two functional groups attached to the N atom. Based on these findings, two efficient and general methods for the synthesis of highly valuable 3‐indolyl aldehydes and 3‐azabicyclo[3,1,0]hexyl aldehydes have been developed.