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

A method for the regioselective functionalization of haloarenes through deprotonative lithiation is disclosed. The generated haloaryllithiums were trapped in a batch reactor with a zinc chloride diamine complex to provide organozinc species without aryne formation, which reacted with electrophiles to afford the corresponding products in 38−98% yields. This method was applied to the five-step total synthesis of carbazomycin A on a gram scale in 33% overall yield.

The selective trapping of multiple transient azolyllithiums in a' halogen dance' was realized in ab atch reactor,b yc hoosing an appropriate zinc halide diamine complex as the transmetalating agent. The concept that the selectivity is switched by the diamine ligand is unprecedented, in contrast to flow chemistry which controls the reaction time precisely.T he reaction is operationally simple and can be performed at 0 8Cw ith high reproducibility on am ultigram scale. These zinc halide diamine complexes are readily available and bench stable, which shows technical advances of this method. The resultant isomeric organozinc reagents were applicable to the divergent syntheses of biologically active azoles in as tereoselective manner. What was the inspiration for this cover design?How to depict the interesting reaction dubbed as the 'halogen dance', which was first proposed in 1971 by the late Professor Joseph F. Bunnett, was the most challenging. This reaction involves short-lived multiple organolithium species from as ingle starting material, which have not been individually trapped so far.T his image means such transient chemical species (dancing on the stage) are successfully snapshotted by the presented method. What was the time-consuming issue in this work?Structural determination of the products was quite tough in this work. In the case of 2,5-dibromothiazole, the iodinated products have no hydrogen atom!T he product ratio was determined by using quantitative 13 CNMR spectroscopy.W ec arefully purified the products and identified their structures by the X-ray crystallographic approach. Besides the iodinated dibromothiazole derivatives, we performed X-ray crystallographic analyses of more than ten products. This process was time-consuming, but we are confident in the accuracy of the chemical structures presented in this study.Invited for the cover of this issuei sK entaro Okano and co-workers at Kobe University.T he image depicts that the 'dancing' transiento rganolithiums in the 'halogen dance' are successfully trapped in ab atch reactor as if their individuals napshots were taken. Read the full text of the articlea t10.1002/chem.202101256.

“Snapshot” trapping of multiple transient azolyllithiums via a halogen ‘dance’ was realized in a batch reactor. This method allows selective generation of isomeric azolylzinc species from a single starting material using newly synthesized bench‐stable zinc halide diamine complexes, leading to the divergent and stereoselective synthesis of functionalized azoles. More information can be found in the Full Paper by K. Okano et al. (DOI: 10.1002/chem.202101256).