A facile, sustainable and eco-friendly protocol has been developed for the halogenation of various heterocycles using TBAX (TBAI/TBAB/TBACl) as halogenating agent, which afforded the products in 90-95% isolated yields. The reaction proceeds with low-cost TBAX and uses greener conditions like EtOH as a solvent and microwave as an alternative energy source for reaction. This protocol has been applied on pyrazoles and extended to different heterocycles like 7-azaindole, indazole, indole and 2-phenylimidazo[1,2α]pyridines. The gram-scale iodination reaction has also been successfully performed by optimizing conventional heating conditions, which demonstrates its potential applicability in organic synthesis. Further these halogenated pyrazoles have been utilized for different coupling reactions including formation of arylated, alkynylated and sulfenated pyrazoles. However, TBAF mediated fluorination did not work.

The insertion of selenium was achieved in the form of mono-selenides and di-selenides for the preparation of novel bis-heterocyclic compounds. This method is more general and provides scaffold diversity with high yields of products. The concentration-dependent mono- and di-selenylation reaction selectivity was achieved using SeO 2 as an efficient selenylating reagent.