Rhodium(II)‐Catalyzed Denitrogenative Transformations of N‐Sulfonyl‐1,2,3‐Triazoles

N‐Sulfonyl‐1,2,3‐triazoles are valuable precursors for the generation of α‐imino carbene intermediates in the presence of the metal catalysts, especially rhodium(II) complexes. Due to the presence of electrophilic carbene and nucleophilic nitrogen, these reactive intermediates can easily be incorporated into many annulations, cycloadditions, C−H or O/N/S−H bond insertions and functionalization reactions. A large number of pharmaceutically important nitrogen‐based building blocks can be constructed via this direct and atom‐economical carbene strategy. In this review, we have described the transformations of N‐sulfonyl‐1,2,3‐triazoles based on α‐imino rhodium(II) carbene intermediates. N‐Sulfonyl‐1,2,3‐triazoles have emerged as a powerful tool for many annulations, X−H bond insertions or functionalizations under rhodium catalysis. The reaction of N‐sulfonyl‐1,2,3‐triazoles with Rh(II) complexes gives rise to highly electrophilic α‐imino rhodium carbene intermediates that can be readily incorporated to construct various nitrogen‐based building blocks. Considering the significant importance of N‐sulfonyl‐1,2,3‐triazoles in synthetic chemistry, in this review, we have described Rh‐catalyzed transformations of this valuable synthon since 2014.