A TEMPO-mediated [3 + 2] annulation–aromatization protocol for the preparation of pyrazolo­[1,5-a]­pyridines from N-aminopyridines and α,β-unsaturated compounds was developed. The procedure offered multisubstituted pyrazolo­[1,5-a]­pyridines in good to excellent yield with high and predictable regioselectivity. The modification of marketed drugs including Loratadine, Abiraterone, and Metochalcone, and a one-pot three-step gram scale synthesis of key intermediate for the preparation of Selpercatinib were demonstrated. Mechanism studies show that TEMPO serves both as a Lewis acid and as an oxidant.

A series of 2-C-branched glycosyl triazoles including triazole-tethered oligosaccharides and glycopeptides were synthesized in one pot from 1,2-cyclopropanated sugars or 2′-acetonyl-2-O-Ts-C-furanosides, NaN 3 , and alkynes using PEG-400 as a single solvent. Nucleophilic ring-opening azidation of 1,2-cyclopropanated sugars (or 2′-acetonyl group 1,2-migration-azidation of Cfuranosides) obtained glycosyl azides, which upon reaction with alkynes under CuAAC conditions achieved glycosyl triazoles in good yields and high stereoselectivity without the need to change the solvent and isolate any intermediates.