Qin H,
Cai W,
Wang S,
Guo T,
Li G,
Lu H.
*
Nanjing University, P. R. of China
N-Atom Deletion in Nitrogen Heterocycles.
Angew. Chem. Int. Ed. 2021;
60: 20678-20683
DOI:
10.1002/anie.202107356
Key words
nitrogen atom deletion - N-heterocycles - C–C coupling - skeletal editing
Significance
Lu et al. report a versatile method for N-atom excision from N-heterocycles. Rings containing 3–20 members and various types of cyclic structures including carbocycles, O-heterocycles, and N-heterocycles were obtained in moderate to excellent yields.
Comment
The authors propose a mechanism involving an initial N-sulfonylazidonation followed by a Curtius-type rearrangement to generate a 1,1-diazene intermediate. A second rearrangement gives a biradical intermediate that undergoes an intramolecular radical coupling reaction to give the desired product.
