New Combinations of Organic Azides and Adjacent Functional Groups

AbstractThe rapid decay of organic azides with loss of dinitrogen is a very exothermic process and is the reason for the explosive properties of these compounds, which have to be handled carefully if the molecular mass is low. On the other hand, controlled liberation of dinitrogen from azides facilitates the generation of high‐energy intermediates, such as nitrenes, carbenes, strained heterocycles, and many others, that lead to highly valuable products via a diversity of secondary reactions. However, the transformations of organic azides prove to be very important and manifold, even without the loss of dinitrogen. The variety of the succeeding reactions can be further increased when azides with an adjacent functional group are utilized as substrates. Such compounds, for example, polyazidomethanes, geminal azido alcohols, or ethynyl azides, show quite different reactivities when compared with those of simple azides or azides with remote additional functionalities. In several cases, surprising products are thus formed, and the unusual reactivity can also explain why some of these title compounds turned out to be short‐lived intermediates, which were discovered only recently.