Programmable Leaving Group Controlled Skeletal Editing of Pyrroles into Pyridines via Sulfenylcarbenes

Skeletal editing plays a key role in diversifying nitrogen-containing heterocycles and their remodeling. Herein, we present a programmable, leaving-group-controlled single-carbon insertion into pyrroles using sulfenylcarbene. By tuning the leaving group in these sulfenylcarbenes, precise control over functional-group installation through ring expansion was achieved. This methodology was successfully applied to pyrroles, providing access to privileged meta-functionalized pyridines and establishing a platform for the programmable synthesis of pyridine derivatives.