An operationally simple protocol for the rapid and efficient construction of highly substituted 3-hydroxypyridines is presented. The thermally induced cyclization of easily constructed geminal diazides derived from β-ketoesters having an additional olefin moiety affords the title compounds in yields up to 97% under reagent-free conditions. The new method allows for the synthesis of preparative quantities of material. Additionally, the synthetic utility of the pyridine products for the synthesis of valuable heterocycles is described.

In recent years, the development of synthetic methods to afford nitrogen‐containing heterocycles has become increasingly popular. Among these, tetrazoles – an important class of aromatic heterocycles – are of significant interest for example, in medicinal chemistry serving as important bioisosteres. Herein, we present a method to easily access C‐substituted tetrazoles via thermolysis of geminal diazido malonamides. Formation and functionalization of in situ formed isocyanates and corresponding reactions were also studied.