"Snapshot" Trapping of Multiple Transient Azolyllithiums in Batch.

Recent developments in flow microreactor technology have allowed the use of transient organolithium compounds that cannot be realized in a batch reactor. However, trapping of the transient heteroaryllithiums in "halogen dance" is still challenging. We report trapping of such short-lived azolyllithiums in a batch reactor by developing a finely tuned in situ zincation using zinc halide diamine complexes, whose reaction rate is controlled by the appropriate choice of the diamine ligand. The reaction is operationally simple and can be performed at 0 °C with high reproducibility on a multi-gram scale. This method was applicable to a wide range of brominated azoles allowing for deprotonative functionalization, which was used for the concise divergent syntheses of both constitutional isomers of biologically active azoles.