Copper-catalyzed reaction of diazo compounds generates copper carbene intermediates that undergo diverse transformations. In recent years, the selectivity and efficiency of these important conversions have been further improved. In particular, breakthroughs have been made in catalytic asymmetric polar X-H bond insertion reactions. Moreover, novel transformations based on copper carbene, namely copper-catalyzed cross-couplings of diazo compounds, have emerged as powerful methods for carbon-carbon bond formations. This feature article summarizes the most recent developments in this area.

Cu-catalyzed cross-coupling of N-tosylhydrazones with 1,3-azoles leads to the direct C-H benzylation or allylation. Cu carbene migratory insertion is proposed to play the key role in this transformation.

Aryl pyrazolone thioethers were synthesized via the I2-catalysed cross-coupling of pyrazolones with aryl sulphonyl hydrazides in the presence of p-toluenesulphonic acid, which has been proposed to promote the reaction by facilitating the decomposition of sulphonyl hydrazides.

The Pd-catalyzed reaction of N-tosylhydrazones and arylboronic acids provides olefin derivatives. This oxidative cross-coupling is suggested to proceed through a migratory insertion process of a Pd carbene intermediate.