Over the years, we have shown that xanthates and related thiocarbonylthio derivatives allow the generation of radicals under conditions where the radicals possess a considerably increased effective lifetime even in a concentrated medium. Intermolecular additions to un-activated alkenes, as well as a variety of reputedly difficult radical transformations can now be easily accomplished. No metals, heavy or otherwise, are required, and the starting materials and reagents are cheap and readily available. Complex, densely functionalized structures can be constructed in a convergent, modular fashion. In the course of our study of the scope and limitations of this chemistry, we have uncovered a few surprising transformations. Recent results and some mechanistic aspects will be presented and discussed briefly.