Liju Raju, Davide Benedetto Tiz, Adrian Iles, Janez Košmrlj, Ross D. Jansen‐van Vuuren
Six-membered N-heteroarenes ("6NHetAr") play pivotal roles in the pharmaceutical, agrochemical, and materials science industries. In recent times, deuterium (D)-labelled 6NHetAr have demonstrated enhanced performance over their unlabelled counterparts. For example, VV116 and VX-984, approved therapeutics for the treatment of COVID-19 and cancer, and deuterated functional materials for use as ligands in catalysts and organometallic light-emitters. As interest in this field continues to grow, there is a corresponding need to develop more efficient, scalable, and sustainable approaches to deuterate 6NHetAr. In this work, we comprehensively review approaches developed for the incorporation of D into 6NHetAr, their fused counterparts, and complex compounds containing 6NHetAr. We also provide an overview of established and emerging applications for these materials.